Water- and oil-repellent, antistatic composition

ABSTRACT

A water- and oil-repellent, antistatic composition comprises (a) at least one nonpolymeric ionic salt consisting of (i) at least one cation selected from the group consisting of monovalent metal cations, divalent metal cations, and organic onium cations, and (ii) at least one weakly coordinating anion, the conjugate acid of the anion having an acidity greater than or equal to that of a hydrocarbon sulfonic acid, and with the proviso that the anion is organic or fluoroorganic when the cation is a metal; (b) at least one fluorochemical repellency-imparting additive or repellent; and (c) at least one insulating material. The composition exhibits good antistatic and repellency characteristics

[0001] This application is a divisional of U.S. Ser. No. 10/458971,filed Jun. 11, 2003, now allowed, which is a divisional of U.S. Ser. No.09/474711, issued as U.S. Pat. No. 6,592,988, the disclosure of which isherein incorporated by reference.

FIELD OF THE INVENTION

[0002] This invention relates to compositions that exhibit bothrepellency and antistatic characteristics. This invention furtherrelates to fibers, films, fabrics, coatings, and molded or blownarticles comprising the compositions. In other aspects, this inventionalso relates to a topical treatment composition and to processes forimparting both repellency and antistatic characteristics to substrates.

BACKGROUND OF THE INVENTION

[0003] Various fluorochemicals have been used to impart water and oilrepellency, as well as soil resistance, to a variety of substrates (forexample, textiles, carpet, leather, paper, and non-woven webs). Thesefluorochemicals have most often been applied topically (for example, byspraying, padding, or finish bath immersion), but some fluorochemicalshave also been useful as polymer melt additives for preparing water- andoil-repellent polymeric fibers, films, fabrics, etc. The resultingrepellent substrates have found use in numerous applications where waterand/or oil repellency (as well as soil resistance) characteristics havebeen valued.

[0004] For some applications, however, antistatic properties have alsobeen necessary or desirable.

[0005] Electrostatic charge buildup is responsible for a variety ofproblems in the processing and use of many industrial products andmaterials. Electrostatic charging can cause materials to stick togetheror to repel one another. This is a particular problem in fiber andtextile processing. In addition, static charge buildup can cause objectsto attract dirt and dust, thereby decreasing the effectiveness offluorochemical repellents.

[0006] Sudden electrostatic discharges from insulating objects can alsobe a serious problem. With photographic film, such discharges can causefogging and the appearance of artifacts. When flammable materials arepresent (for example, in a surgical environment), a static electricdischarge can serve as an ignition source, resulting in fires and/orexplosions. Static is a particular problem in the electronics industry,since modem electronic devices are extremely susceptible to permanentdamage by static electric discharges.

[0007] However, conventional antistats (many of which are humectantsthat rely on the adsorption and conductivity of water for chargedissipation) have generally not been very effective in combination withfluorochemical repellents. The result of such combination has often beena substantial deterioration (or even elimination) of either antistaticor repellency characteristics (or both), relative to the use of eitheradditive alone.

[0008] Furthermore, it has been particularly difficult to combineconventional antistats and fluorochemical repellents in polymer meltprocessing applications, as, for example, the water associated withhumectant antistats vaporizes rapidly at melt processing temperatures.This has resulted in the undesirable formation of bubbles in the polymerand has caused screw slippage in extrusion equipment. Many antistatshave also lacked the requisite thermal stability, leading to theproduction of objectionable odors (for example, in melt blowingapplications, where high extrusion temperatures are involved).

[0009] Thus, there remains a need in the art for antistatic agents andrepellents that can be effectively combined to impart both goodantistatic characteristics and good repellency characteristics tosubstrates and that, in particular, can be utilized as melt additiveswithout causing processing problems or melt defects.

SUMMARY OF THE INVENTION

[0010] Briefly, in one aspect, this invention provides a water- andoil-repellent, antistatic composition comprising (a) at least onenonpolymeric ionic salt consisting of (i) at least one monovalent metalcation, divalent metal cation, or organic onium cation (for example, aquaternary ammonium ion) and (ii) at least one weakly coordinatinganion, the conjugate acid of the anion having an acidity greater than orequal to that of a hydrocarbon sulfonic acid (for example, abis(perfluoroalkanesulfonyl)imide ion), and with the proviso that theanion is organic or fluoroorganic when the cation is a metal; (b) atleast one fluorochemical repellency-imparting additive or repellent; and(c) at least one insulating material. As used herein, the term “organiconium cation” means a positively charged organic ion having at leastpart of its charge localized on at least one heteroatom (for example,nitrogen, phosphorus, sulfur, iodine, or oxygen). Preferably, theinsulating material is a thermoplastic or thermosetting polymer (morepreferably, thermoplastic), and the composition is prepared by forming ablend (more preferably, a melt blend) of the components.

[0011] It has been discovered that the above-described class of ionicsalt antistatic agents or antistats can be effectively combined withfluorochemical repellents to impart both good antistatic characteristicsand good repellency characteristics to a variety of insulatingmaterials. The antistats and repellents can be combined not only intopical treatments (external additives) but even (and preferably) asmelt additives (internal additives) without causing processing problemsor melt defects. The antistat/repellent combination used in thecomposition of the invention is surprisingly effective at dissipatingthe static charge that can accumulate in an otherwise insulatingsubstrate such as a polymer film or fabric, while also imparting durablewater and oil repellency (and soil resistance). Even more suprisingly,when used in topical treatments or as polymer melt additives inpolypropylene melt-blown nonwoven fabric, certain preferred antistatsexhibit synergistic behavior when combined with the repellent(s), inthat better static dissipation rates are obtained than when theantistats are used alone.

[0012] The combination of ionic salt antistat(s) and fluorochemicalrepellent(s) used in the composition of the invention is compatible witha variety of polymers. Since many of the antistats are hydrophobic(immiscible with water), the antistatic performance of the combinationis often relatively independent of atmospheric humidity levels anddurable even under exposure to aqueous environments. In addition, sincemany of the antistats are stable at temperatures up to 300-500° C., thecombination of such antistat(s) with thermally stable fluorochemicalrepellent(s) is particularly well-suited for use in high temperaturepolymer melt additive applications and in applications where the usetemperatures are very high.

[0013] The combination of ionic salt antistat(s) and fluorochemicalrepellent(s) used in the composition of the invention therefore meetsthe need in the art for antistatic agents and repellents that can beeffectively combined to impart both good antistatic characteristics andgood repellency characteristics to substrates and that, in particular,can be utilized as melt additives without causing processing problems ormelt defects.

[0014] In other aspects, this invention also provides fiber, fabric,film, a coating, and a molded or blown article comprising thecomposition of the invention; processes for imparting both repellencyand antistatic characteristics to a substrate, for example, by bulkaddition or by topical treatment; and a topical treatment compositioncomprising (a) at least one nonpolymeric ionic salt consisting of (i) atleast one monovalent metal cation, divalent metal cation, or organiconium cation and (ii) at least one weakly coordinating anion, theconjugate acid of the anion having an acidity greater than or equal tothat of a hydrocarbon sulfonic acid, and with the proviso that the anionis organic or fluoroorganic when the cation is a metal, and (b) at leastone fluorochemical repellency-imparting additive or repellent.

DETAILED DESCRIPTION OF THE INVENTION

[0015] Antistats

[0016] Ionic salts suitable for use as antistats in the composition ofthe invention are those that consist of a monovalent or divalent metalcation (preferably, monovalent) or an organic onium cation (preferably,an organic onium cation) and a weakly coordinating anion. Suitable metalcations include, for example, lithium, calcium, sodium, potassium,magnesium, zinc, iron, nickel, and copper, with sodium and lithium beingpreferred. The organic onium cation can comprise a heteroatom (forexample, nitrogen, phosphorus, sulfur, iodine, or oxygen; preferably,nitrogen or phosphorus; more preferably, nitrogen) as the charge centeror as a component element in a charge-delocalized chain or ringstructure. The organic onium cation can be cyclic (that is, where thecharge center(s) of the cation are ring atoms) or acyclic (that is,where the charge center(s) of the cation are not ring atoms but can havecyclic substituents). The cyclic cations can be aromatic, unsaturatedbut nonaromatic, or saturated, and the acyclic cations can be saturatedor unsaturated.

[0017] The cyclic cations can contain one or more ring heteroatoms (forexample, nitrogen, oxygen, or sulfur), and the ring atoms can bearsubstituents (for example, hydrogen, halogen, or organic groups such asalkyl, alicyclic, aryl, alkalicyclic, alkaryl, alicyclicalkyl, aralkyl,aralicyclic, and alicyclicaryl groups). Separate alkyl substituents canbe joined together to constitute a unitary alkylene radical of from 2 to4 carbon atoms forming a ring structure. Organic substituents cancontain one or more heteroatoms such as, for example, nitrogen, oxygen,sulfur, phosphorus, or halogen (and thus can be fluoroorganic innature).

[0018] The acyclic cations can have at least one (preferably, at leasttwo; more preferably, at least three; most preferably, four) chargecenter-bonded organic substituents or R groups, with the remainingsubstituents being hydrogen. The R groups can be cyclic or acyclic,saturated or unsaturated, aromatic or nonaromatic, and can contain oneor more heteroatoms such as, for example, nitrogen, oxygen, sulfur,phosphorus, or halogen (and thus can be fluoroorganic in nature).

[0019] Preferably, the organic onium cation is acyclic or unsaturatedcyclic. More preferably, it is acyclic or aromatic, most preferably,acyclic.

[0020] Preferred acyclic organic onium cations are nitrogen onium(ammonium) and phosphorus onium (phosphonium) cations that arequaternary or tertiary (most preferably, quaternary) cations. Thequaternary and tertiary cations are preferably of low symmetry (havingat least two, preferably at least three, different charge center-bondedorganic substituents or R groups as defined above) and more preferablycontain at least one hydroxyl group in at least one charge center-bondedorganic substituent. Most preferred acyclic organic onium cations arethe nitrogen onium cations described below for the ionic salt antistatsof Formula I.

[0021] Preferred aromatic organic onium cations are the nitrogen oniumcations selected from the group consisting of

[0022] wherein R₁, R₂, R₃, R₄, R₅, and R₆ are independently selectedfrom the group consisting of H, F, alkyl groups of from 1 to about 18carbon atoms (preferably, from 1 to about 11 carbon atoms), two saidalkyl groups joined together to form a unitary alkylene radical of from2 to 4 carbon atoms forming a ring structure, and phenyl groups; andwherein said alkyl groups, alkylene radicals, or phenyl groups cancomprise one or more substituent groups (preferably, a group that iscapable of hydrogen bonding, for example, an amino, hydroxyl, acetyl, oracetamide group, or an electron-withdrawing group, for example, F—, Cl—,CF₃—, SF₅—, CF₃S—, (CF₃)₂CHS—, and (CF₃)₃ CS—).

[0023] Preferred unsaturated cyclic, nonaromatic organic onium cationsinclude the nitrogen onium cations represented by the following formula

[0024] where R₁, R₂, R₃, R₄, R₅, R₆, and R₇ are defined as R₁, R₂, R₃,R₄, R₅, and R₆ are defined above for the preferred aromatic organiconium cations.

[0025] Suitable weakly coordinating anions have a conjugate acid that isat least as acidic as a hydrocarbon sulfonic acid (preferably, ahydrocarbon sulfonic acid having from 1 to about 20 carbon atoms; morepreferably, an alkane, aryl, or alkaryl sulfonic acid having from 1 toabout 8 carbon atoms; even more preferably, methane or p-toluenesulfonic acid; most preferably, p-toluene sulfonic acid). Preferably,the conjugate acid is a strong acid. More preferably, the Hammettacidity function, H₀, of the neat conjugate acid of the anion is lessthan about −7 (most preferably, less than about −10).

[0026] Representative examples of suitable weakly coordinating anionsinclude BF₄—; PF₆—; SbF₆—; AsF₆—; ClO₄—; NO₃—; Cl—; Br—; F—; HSO₄—;H₂PO₄—; organic anions such as alkane, aryl, and alkaryl sulfonates;fluorinated and unfluorinated tetraarylborates; carboranes and halogen-,alkyl-, or haloakyl-substituted carborane anions includingmetallocarborane anions; teflates (for example, —OTeF₅, —B(OTeF₅)₄, and—Pd(OTeF₅)₄); and fluoroorganic anions such asperfluoroalkanesulfonates, cyanoperfluoroalkanesulfonylamides,bis(cyano)perfluoroalkanesulfonylmethides,bis(perfluoroalkanesulfonyl)imides,bis(perfluoroalkanesulfonyl)methides, andtris(perfluoroalkanesulfonyl)methides; and the like. Preferred anionsinclude organic and fluoroorganic anions (more preferably, alkane, aryl,and alkaryl sulfonates, as well as perfluoroalkanesulfonates,bis(perfluoroalkanesulfonyl)imides, andtris(perfluoroalkanesulfonyl)methides; most preferably, alkanesulfonates, perfluoroalkanesulfonates, andbis(perfluoroalkanesulfonyl)imides).

[0027] The fluoroorganic anions can be either fully fluorinated, that isperfluorinated, or partially fluorinated (within the organic portionthereof). Preferred fluoroorganic anions include those that comprise atleast one highly fluorinated alkanesulfonyl group, that is, aperfluoroalkanesulfonyl group or a partially fluorinated alkanesulfonylgroup wherein all non-fluorine carbon-bonded substituents are bonded tocarbon atoms other than the carbon atom that is directly bonded to thesulfonyl group (preferably, all non-fluorine carbon-bonded substituentsare bonded to carbon atoms that are more than two carbon atoms away fromthe sulfonyl group).

[0028] Preferably, the fluoroorganic anion is at least about 80 percentfluorinated (that is, at least about 80 percent of the carbon-bondedsubstituents of the anion are fluorine atoms). More preferably, theanion is perfluorinated (that is, fully fluorinated, where all of thecarbon-bonded substituents are fluorine atoms). The anions, includingthe preferred perfluorinated anions, can contain one or more catenary(that is, in-chain) heteroatoms such as, for example, nitrogen, oxygen,or sulfur.

[0029] Preferred fluoroorganic anions include perfluoroalkanesulfonates,bis(perfluoroalkanesulfonyl)imides, andtris(perfluoroalkanesulfonyl)methides. The perfluoroalkanesulfonates andbis(perfluoroalkanesulfonyl)imides are more preferred anions, with theperfluoroalkanesulfonates being most preferred.

[0030] The ionic salt antistats can be solids or liquids under useconditions but preferably have melting points less than about 150° C.(more preferably, less than about 50° C.; most preferably, less thanabout 25° C.). Liquid ionic salts are preferred due to their generallybetter static dissipative performance. For use as polymer meltadditives, the ionic salt antistats are preferably stable attemperatures of about 250° C. and above (more preferably, about 300° C.and above) and are preferably miscible with the insulating material atthe melt processing temperature. (In other words, the onset ofdecomposition of the antistats is above such temperatures.) Preferredionic salt antistats for polymer melt additive applications includethose having cations selected from the group consisting of alkylphosphonium cations, aromatic nitrogen onium cations (preferably, thepreferred aromatic organic onium cations set forth above), and acyclicnitrogen onium cations (preferably, the cations shown in Formula Ibelow); and having organic or fluoroorganic anions (preferably, anionsselected from the group consisting of alkane sulfonates, arylsulfonates, alkaryl sulfonates, perfluoroalkanesulfonates,bis(perfluoroalkanesulfonyl)imides, andtris(perfluoroalkanesulfonyl)methides; more preferably, alkanesulfonates, perfluoroalkanesulfonates, andbis(perfluoroalkanesulfonyl)imides); most preferably,perfluoroalkanesulfonates and bis(perfluoroalkanesulfonyl)imides.

[0031] The antistats are also preferably hydrophobic. Thus, a preferredclass of ionic salt antistats for use in the composition of theinvention includes those that consist of (a) an aromatic nitrogen oniumcation selected from the group consisting of

[0032] wherein R₁, R₂, R₃, R₄, R₅ and R₆ are independently selected fromthe group consisting of H, F, alkyl groups of from 1 to about 18 carbonatoms (preferably, from 1 to about 11 carbon atoms), two said alkylgroups joined together to form a unitary alkylene radical of from 2 to 4carbon atoms forming a ring structure, and phenyl groups; and whereinsaid alkyl groups, alkylene radicals, or phenyl groups can comprise oneor more substituent groups (preferably, an electron-withdrawing group,for example, F—, Cl—, CF₃—, SF₅—, CF₃S—, (CF₃)₂CHS—, and (CF₃)₃ CS—);and (b) a weakly coordinating fluoroorganic anion in accordance with theabove description or a weakly coordinating anion selected from the groupconsisting of BF₄—, PF₆—, AsF₆—, and SbF₆—. This preferred classcomprises a most preferred subclass of the hydrophobic ionic liquidsdescribed in U.S. Pat. No. 5,827,602 (Koch et al.), the description ofthe members of which is incorporated herein by reference.

[0033] Another preferred class of ionic salt antistats useful inpreparing the composition of the invention is the class of compoundsrepresented by Formula I below

(R₁)_(4-z)N⁺[(CH₂)_(q)OR₂]_(z)X⁻  (I)

[0034] wherein each R₁ is independently selected from the groupconsisting of alkyl, alicyclic, aryl, alkalicyclic, alkaryl,alicyclicalkyl, aralkyl, aralicyclic, and alicyclicaryl moieties thatcan contain one or more heteroatoms such as, for example, nitrogen,oxygen, sulfur, phosphorus, or halogen (and thus can be fluoroorganic innature); each R₂ is independently selected from the group consisting ofhydrogen and the moieties described above for R₁; z is an integer of 1to 4; q is an integer of 1 to 4; and X is a weakly coordinating alkanesulfonate, aryl sulfonate, alkaryl sulfonate, or fluoroorganic anion asdescribed above (preferably, a fluoroorganic anion). R₁ is preferablyalkyl, and R₂ is preferably selected from the group consisting ofhydrogen, alkyl, and acyl (more preferably, hydrogen or acyl; mostpreferably, hydrogen). Most preferably, z is 1, q is 2, R₁ is alkyl, andR₂ is hydrogen.

[0035] Many of the above-described ionic salt antistats (for example,metal bis(perfluoroalkanesulfonyl)imides, metalperfluoroalkanesulfonates, onium halides, onium alkanesulfonates, oniumarylsulfonates, onium tetrafluoroborates, and oniumhexafluorophosphates) are commercially available and can also beprepared by standard methods known in the art. Other ionic saltantistats comprising an organic onium cation can be prepared by ionexchange or metathesis reactions, which are also well known in the art.For example, a precursor onium salt can be combined with a precursormetal salt or the corresponding acid of a weakly coordinating anion inaqueous solution. Upon combining, the desired product (the onium salt ofthe weakly coordinating anion) precipitates (as a liquid or solid) orcan be preferentially extracted into an organic solvent (for example,methylene chloride). The product can be isolated by filtration or byliquid/liquid phase separation, can be washed with water to completelyremove byproduct metal salt or acid (if present), and can then be driedthoroughly under vacuum to remove all volatiles (including water andorganic solvent, if present). Similar metathesis reactions can beconducted in organic solvents (for example, acetonitrile) rather than inwater, and, in this case, the salt byproduct generally preferentiallyprecipitates, while the desired product salt remains dissolved in theorganic solvent (from which it can be isolated using standardexperimental techniques).

[0036] Weakly coordinating fluoroorganic anions (for use in preparingsuch ionic salts) can be prepared by standard methods known in the art,and metal salts of many are commercially available. Such methods includethe anion precursor preparative methods described in the followingreferences, the descriptions of which are incorporated herein byreference: imide precursors—U.S. Pat. No. 5,874,616 (Howells et al.),U.S. Pat. No. 5,723,664 (Sakaguchi et al.), U.S. Pat. No. 5,072,040(Armand), and U.S. Pat. No. 4,387,222 (Koshar); methide precursors—U.S.Pat. No. 5,554,664 (Lamanna et al.) and U.S. Pat. No. 5,273,840(Dominey); sulfonate precursors—U.S. Pat. No. 5,176,943 (Wou), U.S. Pat.No. 4,582,781 (Chen et al.), U.S. Pat. No. 3,476,753 (Hanson), and U.S.Pat. No. 2,732,398 (Brice et al.); sulfonate, imide, and methideprecursors having caternary oxygen or nitrogen in a fluorochemicalgroup—U.S. Pat. No. 5,514,493 (Waddell et al.); disulfone precursors—R.J. Koshar and R. A. Mitsch, J. Org. Chem., 38, 3358 (1973) and U.S. Pat.No. 5,136,097 (Armand).

[0037] In general, cyano-containing methides and amides containingfluoroalkanesulfonyl groups can be prepared by the reaction offluoroalkanesulfonyl fluorides, R_(f)SO₂F, with anhydrous malononitrileor cyanamide, respectively, in the presence of a non-nucleophilic base.This synthetic procedure is described in Scheme 1 of U.S. Pat. No.5,874,616 (Howells et al.) for the preparation ofbis(fluoroalkanesulfonyl)imides (the description of which isincorporated herein by reference) and involves the substitution ofeither malononitrile or cyanamide for the fluoroalkanesulfonamide. Theresulting intermediate non-nucleophilic base cation-containing methideor amide salt can be converted to the desired cation salt (typicallylithium) via standard metathesis reactions well known in the art.

[0038] Representative examples of useful ionic salt antistats includeoctyldimethyl-2-hydroxyethylammonium bis(trifluoromethylsulfonyl)imide:[C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻N(SO₂CF₃)₂],octyldimethyl-2-hydroxyethylammonium perfluorobutanesulfonate:[C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻OSO₂C₄F₉], octyldimethyl-2-hydroxyethylammoniumtrifluoromethanesulfonate: [C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻OSO₂CF₃],octyldimethyl-2-hydroxyethylammoniumtris(trifluoromethanesulfonyl)methide: [C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH⁻C(SO₂CF₃)₃], trimethyl-2-acetoxyethylammoniumbis(trifluoromethylsulfonyl)imide: [(CH₃)₃N⁺CH₂CH₂OC(O)CH3 ⁻N(SO₂CF₃)₂],trimethyl-2-hydroxyethylammonium bis(perfluorobutanesulfonyl)imide:[(CH₃)₃N⁺CH₂OH ⁻N(SO₂C₄F₉)₂], triethylammoniumbis(perfluoroethanesulfonyl)imide: [Et₃N⁺H ⁻N(SO₂C₂F₅)₂],tetraethylammonium trifluoromethanesulfonate: [CF₃SO₃ ⁻ ⁺NEt₄],tetraethylammonium bis(trifluoromethanesulfonyl)imide: [(CF₃SO₂)₂N⁻⁺NEt₄], tetramethylammonium tris(trifluoromethanesulfonyl)methide:[(CH₃)₄N⁺ ⁻C(SO₂CF₃)₃], tetrabutylammoniumbis(trifluoromethanesulfonyl)imide: [(C₄H₉)₄N⁺ ⁻N(SO₂CF₃)₂],trimethyl-3-perfluorooctylsulfonamidopropylammoniumbis(trifluoromethanesulfonyl)imide: [C₈F₁₇SO₂NH(CH₂)₃N⁺(CH₃)₃⁻N(SO₂CF₃)₂], 1-hexadecylpyridinium bis(perfluoroethanesulfonyl)imide:[n-C₁₆H₃₃-cyc-N⁺C₅H₅ ⁻N(SO₂C₂F₅)₂], 1-hexadecylpyridiniumperfluorobutanesulfonate: [n-C₁₆H₃₃-cyc-N⁺C₅H₅ ⁻OSO₂C₄F₉],1-hexadecylpyridinium perfluorooctanesulfonate: [n-C₁₆H₃₃-cyc-N⁺C₅H₅⁻OSO₂C₈F₁₇], n-butylpyridinium bis(trifluoromethanesulfonyl)imide:[n-C₄H₉-cyc-N⁺C₅H₅ ⁻N(SO₂CF₃)₂], n-butylpyridiniumperfluorobutanesulfonate: [n-C₄H₉-cyc-N⁺C₅H₅ ⁻OSO₂C₄F₉],1,3-ethylmethylimidazolium bis(trifluoromethanesulfonyl)imide:[CH₃-cyc-(N⁺C₂H₂NCH)CH₂CH₃ ⁻N(SO₂CF₃)₂], 1,3-ethylmethylimidazoliumnonafluorobutanesulfonate: [CH₃-cyc-(N⁺C₂H₂NCH)CH₂CH₃ ⁻OSO₂C₄F₉],1,3-ethylmethylimidazolium trifluoromethanesulfonate:[CH₃-cyc-(N⁺C₂H₂NCH)CH₂CH₃ ⁻OSO₂CF₃], 1,3-ethylmethylimidazoliumhexafluorophosphate: [CH₃-cyc-(N⁺C₂H₂NCH)CH₂CH₃ PF₆ ⁻],1,3-ethylmethylimidazolium tetrafluoroborate: [CH₃-cyc-(N⁺C₂H₂NCH)CH₂CH₃BF₄ ⁻], lithium perfluorobutanesulfonate: [Li⁺ ⁻OSO₂C₄F₉], lithiumtrifluoromethanesulfonate: [Li⁺ ⁻OSO₂CF₃], lithiumbis(trifluoromethanesulfonyl)imide: [Li⁺ ⁻N(SO₂CF₃)₂], lithiumtris(trifluoromethanesulfonyl)methide: [Li⁺ ⁻C(SO₂CF₃)₃], sodiumphenylbis(trifluoromethanesulfonyl)methide: [Na⁺ ⁻C(C₆H₅)(SO₂CF₃)₂],octyldimethyl-2-hydroxyethylammonium teflate: [C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH⁻OTeF₅], lithium permethylmonocarba-closo-dodecaborate: [Li⁺⁻CB₁₁(CH₃)₁₂], sodium monocarba-closo-dodecaborate: [Na⁺ ⁻CB₁₁H₂],sodium tetrakis-(pentafluorophenyl)borate: [Na⁺ ⁻B(C₆F₅)₄],octyldimethyl-2-hydroxyethylammonium methanesulfonate:[C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻OSO₂CH₃], tetrabutylphosphoniumperfluorobutanesulfonate: [(C₄H₉)₄P⁺ ⁻OSO₂C₄F₉], tetraphenylphosphoniumbis(trifluoromethanesulfonyl)imide: [(C₆H₅)₄P⁺ ⁻N(SO₂CF₃)₂],trioctylmethylammonium chloride: [(C₈H₁₇)₃(CH₃)N⁺Cl⁻],trioctylmethylammonium trifluoromethanesulfonate: [(C₈H₁₇)₃(CH₃)N⁺⁻OSO₂CF₃], trioctylmethylammonium perfluorobutanesulfonate:[(C₈H₁₇)₃(CH₃)N⁺ ⁻OSO₂C₄F₉],3-(2-hydroxyethyl)-1-methyl-2-undecylimidazolinium p-toluenesulfonate:[CH₃-cyc-(N⁺C₂H₄N(CH₂CH₂OH)C)C₁₁H₂₃ ⁻OSO₂C₆H₄CH₃],1-dodecyl-2-ethyl-3-(2-hydroxyethyl)imidazolinium p-toluenesulfonate:[C₁₂H₂₅-cyc-(N⁺C₂H₄N(CH₂CH₂OH)C)C₂H₅ ⁻OSO₂C₆H4CH₃],1,2-dimethyl-3-propylimidazolium bis(trifluoromethanesulfonyl)imide,1,2-dimethyl-3-propylimidazolium tris(trifluoromethanesulfonyl)methide,1,2-dimethyl-3-propylimidazolium trifluoromethanesulfonylperfluorobutanesulfonylimide, 1-ethyl-3-methylimidazoliumcyanotrifluoromethanesulfonylamide, 1-ethyl-3-methylimidazoliumbis(cyano)trifluoromethanesulfonylmethide, 1-ethyl-3-methylimidazoliumtrifluoromethanesulfonylperfluorobutanesulfonylimide,octyldimethyl-2-hydroxyethylammoniumtrifluoromethylsulfonylperfluorobutanesulfonylimide,2-hydroxyethyltrimethylammoniumtrifluoromethylsulfonylperfluorobutanesulfonylimide,2-methoxyethyltrimethylammonium bis(trifluoromethanesulfonyl)imideoctyldimethyl-2-hydroxyethylammoniumbis(cyano)trifluoromethanesulfonylmethide,trimethyl-2-acetoxyethylammoniumtrifluoromethylsulfonylperfluorobutanesulfonylimide, 1-butylpyridiniumtrifluoromethylsulfonylperfluorobutanesulfonylimide,2-ethoxyethyltrimethylammonium trifluoromethanesulfonate,1-butyl-3-methylimidazolium perfluorobutanesulfonate,perfluoro-1-ethyl-3-methylimidazoliumbis(trifluoromethanesulfonyl)imide, 1-ethyl-2-methylpyrazoliumperfluorobutanesulfonate, 1-butyl-2-ethylpyrazoliumtrifluoromethanesulfonate, N-ethylthiazoliumbis(trifluoromethanesulfonyl)imide, N-ethyloxazoliumbis(trifluoromethanesulfonyl)imide, and 1-butylpyrimidiniumperfluorobutanesulfonylbis(trifluoromethanesulfonyl)-methide,1,3-ethylmethylimidazolium hexafluorophosphate,1,3-ethylmethylimidazolium tetrafluoroborate, and mixtures thereof.

[0039] Preferred ionic salt antistats includeoctyldimethyl-2-hydroxyethylammonium bis(trifluoromethylsulfonyl)imide:[C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻N(SO₂CF₃)₂],octyldimethyl-2-hydroxyethylammonium perfluorobutanesulfonate:[C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻OSO₂C₄F₉], octyldimethyl-2-hydroxyethylammoniumtrifluoromethanesulfonate: [C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻OSO₂CF₃],octyldimethyl-2-hydroxyethylammoniumtris(trifluoromethanesulfonyl)methide: [C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH⁻C(SO₂CF₃)₃], trimethyl-2-acetoxyethylammoniumbis(trifluoromethylsulfonyl)imide: [(CH₃)₃N⁺CH₂CH₂OC(O)CH3 ⁻N(SO₂CF₃)₂],trimethyl-2-hydroxyethylammonium bis(perfluorobutanesulfonyl)imide:[(CH₃)₃N⁺CH₂CH₂OH ⁻N(SO₂C₄F₉)₂], triethylammoniumbis(perfluoroethanesulfonyl)imide: [Et₃N⁺H ⁻N(SO₂C₂F₅)₂],tetraethylammonium trifluoromethanesulfonate: [CF₃SO₃ ⁻ ⁺NEt₄],tetraethylammonium bis(trifluoromethanesulfonyl)imide: [(CF₃SO₂)₂N⁻⁺NEt₄], tetramethylammonium tris(trifluoromethanesulfonyl)methide:[(CH₃)₄N⁺ ⁻C(SO₂CF₃)₃], tetrabutylammoniumbis(trifluoromethanesulfonyl)imide: [(C₄H₉)₄N⁺ ⁻N(SO₂CF₃)₂],trimethyl-3-perfluorooctylsulfonamidopropylammoniumbis(trifluoromethanesulfonyl)imide: [C₈F₁₇SO₂NH(CH₂)₃N⁺(CH₃)₃⁻N(SO₂CF₃)₂], 1-hexadecylpyridinium bis(perfluoroethanesulfonyl)imide:[n-C₁₆H₃₃-cyc-N⁺C₅H₅ ⁻N(SO₂C₂F₅)₂], 1-hexadecylpyridiniumperfluorobutanesulfonate: [n-C₁₆H₃₃-cyc-N⁺C₅H₅ ⁻OSO₂C₄F₉],1-hexadecylpyridinium perfluorooctanesulfonate: [n-C₁₆H₃₃-cyc-N⁺C₅H₅⁻OSO₂C₈F₇], n-butylpyridinium bis(trifluoromethanesulfonyl)imide:[n-C₄H₉-cyc-N⁺C₅H₅ ⁻N(SO₂CF₃)₂], n-butylpyridiniumperfluorobutanesulfonate: [n-C₄H₉-cyc-N⁺C₅H₅ ⁻OSO₂C₄F₉],1,3-ethylmethylimidazolium bis(trifluoromethanesulfonyl)imide:[CH₃-cyc-(N⁺C₂H₂NCH)CH₂CH₃ ⁻N(SO₂CF3)₂], 1,3-ethylmethylimidazoliumnonafluorobutanesulfonate: [CH₃-cyc-(N⁺C₂H₂NCH)CH₂CH₃ ⁻OSO₂C₄F₉],1,3-ethylmethylimidazolium trifluoromethanesulfonate:[CH₃-cyc-(N⁺C₂H₂NCH)CH₂CH₃ ⁻OSO₂CF₃], lithium perfluorobutanesulfonate:[Li⁺ ⁻OSO₂C₄F₉], lithium trifluoromethanesulfonate: [Li⁺ ⁻OSO₂CF₃],lithium bis(trifluoromethanesulfonyl)imide: [Li⁺N(SO₂CF₃)₂],tetrabutylphosphonium perfluorobutanesulfonate: [(C₄H₉)₄P⁺ ⁻OSO₂C₄F₉],octyldimethyl-2-hydroxyethylammonium methanesulfonate:[C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻OSO₂CH₃],1-dodecyl-2-ethyl-3-(2-hydroxyethyl)imidazolinium p-toluenesulfonate:[C₁₂H₂₅-cyc-(N⁺C₂H₄N(CH₂CH₂OH)C)C₂H₅ ⁻OSO₂C₆H₄CH₃],1,3-ethylmethylimidazolium tetrafluoroborate, and mixtures thereof.

[0040] More preferred ionic salt antistats includeoctyldimethyl-2-hydroxyethylammonium bis(trifluoromethylsulfonyl)imide,octyldimethyl-2-hydroxyethylammonium perfluorobutanesulfonate,octyldimethyl-2-hydroxyethylammonium trifluoromethanesulfonate,triethylammonium bis(perfluoroethanesulfonyl)imide, tetraethylammoniumtrifluoromethanesulfonate,trimethyl-3-perfluorooctylsulfonamidopropylammoniumbis(trifluoromethanesulfonyl)imide, 1,3-ethylmethylimidazoliumnonafluorobutanesulfonate, 1,3-ethylmethylimidazoliumbis(trifluoromethanesulfonyl)imide, 1,3-ethylmethylimidazoliumtrifluoromethanesulfonate, tetrabutylphosphoniumperfluorobutanesulfonate, and mixtures thereof.

[0041] Most preferred ionic salt antistats includeoctyldimethyl-2-hydroxyethylammonium bis (trifluoromethylsulfonyl)imide,octyldimethyl-2-hydroxyethylammonium trifluoromethanesulfonate,octyldimethyl-2-hydroxyethylammonium nonafluorobutanesulfonate,triethylammonium bis(perfluoroethanesulfonyl)imide,1,3-ethylmethylimidazolium nonafluorobutanesulfonate,1,3-ethylmethylimidazolium bis(trifluoromethanesulfonyl)imide,1,3-ethylmethylimidazolium trifluoromethanesulfonate,tetrabutylphosphonium perfluorobutanesulfonate, and mixtures thereof,with further preferences being in accordance with the general cation andanion preferences set forth above.

[0042] Fluorochemical Repellents

[0043] Suitable fluorochemical repellency-imparting additives orrepellents for use in the composition of the invention are those thatcomprise at least one fluorochemical group, preferably, at least onefluoroaliphatic or fluoroalicyclic group. Such fluorochemicals includeany of the fluorochemical group-containing polymeric and oligomericcompounds known in the art to impart water and oil repellency tosubstrates. These polymeric and oligomeric fluorochemicals typicallycomprise one or more fluorochemical groups that contain a perfluorinatedcarbon chain having from 3 to about 20 carbon atoms, more preferablyfrom about 4 to about 12 carbon atoms. These fluorochemical groups cancontain straight chain, branched chain, or cyclic fluorinated alkylenegroups or any combination thereof. The fluorochemical groups canoptionally contain catenary (i.e., in-chain) heteroatoms such as oxygen,divalent or hexavalent sulfur, or nitrogen. Fully-fluorinated groups arepreferred, but hydrogen or chlorine atoms can also be present assubstituents, provided that no more than one atom of either is presentfor every two carbon atoms. It is additionally preferred that anyfluorochemical group contain at least about 40% fluorine by weight, morepreferably at least about 50% fluorine by weight. The terminal portionof the group is generally fully-fluorinated, preferably containing atleast 7 fluorine atoms, e.g., CF₃CF₂CF₂—, (CF₃)₂CF—, SF₅CF₂—.Perfluorinated aliphatic groups (i.e., those of the formulaC_(n)F_(2n+1)—) are the most preferred fluorochemical groups.

[0044] Representative examples of suitable fluorochemicals includefluorochemical urethanes, ureas and substituted ureas, esters, ethers,alcohols, epoxides, allophanates, amides, amines (and salts thereof),acids (and salts thereof), carbodiimides, guanidines, oxazolidinones,isocyanurates, piperazines, aminoalcohols, sulfones, imides, biurets,acrylate and methacrylate homopolymers and copolymers, siloxanes,alkoxysilanes, chlorosilanes, and mixtures thereof.

[0045] Representative fluorochemical group-containing polymers useful inthe present invention include fluorochemical acrylate and methacrylatehomopolymers or copolymers containing fluorochemical acrylate monomersinterpolymerized with monomers such as methyl methacrylate, butylacrylate, octadecylmethacrylate, acrylate and methacrylate esters ofoxyalkylene and polyoxyalkylene polyol oligomers (e.g., oxyethyleneglycol dimethacrylate, polyoxyethylene glycol dimethacrylate, methoxyacrylate, and polyoxyethylene acrylate), glycidyl methacrylate,ethylene, butadiene, styrene, isoprene, chloroprene, vinyl acetate,vinyl chloride, vinylidene chloride, vinylidene fluoride, acrylonitrile,vinyl chloroacetate, vinylpyridine, vinyl alkyl ethers, vinyl alkylketones, acrylic acid, methacrylic acid, 2-hydroxyethylacrylate,N-methylolacrylamide, 2-(N,N,N-trimethylammonium)ethyl methacrylate, and2-acrylamido-2-methylpropanesulfonic acid (AMPS). The relative amountsof various comonomers used can generally be selected empirically,depending on the substrate to be treated, the properties desired, andthe mode of application to the substrate. Useful fluorochemicals alsoinclude blends of the various fluorochemicals described above.

[0046] Also useful in the present invention are blends offluorochemicals with fluorine-free extender compounds, such assiloxanes, (meth)acrylate and substituted acrylate polymers andcopolymers, N-methylolacrylamide-containing acrylate polymers,urethanes, blocked isocyanate-containing polymers and oligomers,condensates or precondensates of urea or melamine with formaldehyde,glyoxal resins, condensates of fatty acids with melamine or ureaderivatives, condensates of fatty acids with polyamides and theirepichlorohydrin adducts, waxes, polyethylene, chlorinated polyethylene,alkyl ketene dimers, esters, and amides. Blends of these fluorine-freeextender compounds can also be used. The relative amount of extendercompound to fluorochemical is not critical. However, the overallcomposition of the fluorochemical treatment generally contains, relativeto the amount of solids present in the system, at least about 3 weightpercent, preferably at least about 5 weight percent, carbon-boundfluorine in the form of said fluorochemical groups.

[0047] Many fluorochemicals, including blends that include fluorine-freeextender molecules such as those described above, are commerciallyavailable as ready-made formulations. Such products are sold, forexample, as Scotchgard™ brand Carpet Protector (manufactured by 3M Co.,Saint Paul, Minn.) and as Zonyl™ brand Carpet Treatment (manufactured byE.I. du Pont de Nemours and Company, Wilmington, Del.).

[0048] Useful fluorochemicals are described in European Pat. No. 0 613462 (Minnesota Mining and Manufacturing Company) and in U.S. Pat. No.3,728,151 (Sherman et al.), U.S. Pat. No. 3,816,229 (Bierbrauer), U.S.Pat. No. 3,896,035 (Schultz et al.), U.S. Pat. No. 3,901,727 (Loudas),U.S. Pat. No. 3,916,053 (Sherman et al.), U.S. Pat. No. 4,043,923(Loudas), U.S. Pat. No. 4,043,964 (Sherman et al.), U.S. Pat. No.4,264,484 (Patel), U.S. Pat. No. 4,624,889 (Bries), U.S. Pat. No.5,274,159 (Pellerite et al.), U.S. Pat. No. 5,380,778 (Buckanin), andU.S. Pat. No. 5,451,622 (Boardman et al.), the descriptions of which areincorporated herein by reference.

[0049] Fluorochemical repellents suitable for use as polymer meltadditives are preferably stable at temperatures of 250° C. and above(more preferably, 300° C. and above), are preferably miscible with theinsulating material at the melt processing temperature, and arepreferably capable of migration to the surface of the insulatingmaterial. Thus, a preferred class of fluorochemical repellents, usefulboth in topical treatments and as polymer melt (or other bulk polymer)additives, includes fluorochemical oxazolidinone compositions orfluorochemical oxazolidinones comprising normally solid,water-insoluble, fluoroaliphatic radical-containing 2-oxazolidinonecompounds, the compounds comprising one or more 2-oxazolidinonemoieties,

[0050] at least one of which has a monovalent fluoroaliphatic radical,R_(f), bonded to the 5-position carbon atom thereof by an organiclinking group.

[0051] A preferred subclass of such fluoroaliphatic radical-containingoxazolidinone compounds is that represented by Formula II below:

[0052] where each R¹ is independently hydrogen or an organic radical,which organic radical can contain -Q-R_(f) where Q is a linking groupand R_(f) is a fluoroaliphatic radical that can optionally contain oneor more catenary (in-chain) heteroatoms such as oxygen; each R² isindependently an organic radical, which organic radical can contain-Q-R_(f) where Q and R_(f) are as defined above; with the proviso thatthere is at least one R_(f) radical in one of R¹ and R²; each A isindependently an organic radical; a is zero or 1; b is a number from 0to about 6; c is 0, 1, or 2; and the sum of a+b+c is at least 1.Preferably, R₁ is an organic radical that contains -QR_(f), where R_(f)is a perfluoroalkyl group having from about 3 to about 20 carbon atoms(preferably, from about 4 to about 12 carbon atoms), and Q comprises aheteroatom-containing group, an organic group, or a combination thereof(preferably, Q is —SO₂N(R′)(CH₂)_(k)—, —(CH₂)_(k)—, —CON(R′)(CH₂)_(k)—,or —(CH₂)_(k)SO₂N(R′)(CH₂)_(k)—, where R′ is hydrogen, phenyl, or ashort chain (up to about 6 carbon atoms) alkyl group (preferably, methylor ethyl), and each k is independently an integer from 1 to about 20); ais 1; b is 0; c is 0; and A is an alkyl group having from about 12 toabout 22 carbon atoms. Formula II represents individual compounds ormixtures of compounds, for example, as they are obtained as productsfrom reactions used in their preparation.

[0053] Such fluorochemical oxazolidinone compositions can be preparedusing known organic reactions, for example, by the reaction of epoxidesor halohydrins (for example, chlorohydrins or bromohydrins) with organicisocyanates in each which reaction at least one of the reactantscontains an R_(f) radical. The reactions can be carried out stepwise byreacting the halohydrin with the isocyanate under urethane bond-formingconditions, for example, 20° C. to 100° C. for about 1 to 24 hours, toform a urethane intermediate, followed by addition of a base andreaction at about 20° C. to 100° C. for about 1 to 24 hours to form theoxazolidinone composition. Alternatively, an epoxide can be reacted withan isocyanate in the presence of a catalyst, such as diethyl zinc, toform the oxazolidinone directly.

[0054] Suitable fluorochemical oxazolidinones and methods for theirpreparation are further described in U.S. Pat. Nos. 5,025,052 and5,099,026 (Crater et al.), the descriptions of which are incorporatedherein by reference.

[0055] Other preferred fluorochemical repellents, useful both in topicaltreatments and as polymer melt (or other bulk polymer) additives,include those described in U.S. Pat. No. 3,899,563 (Oxenrider et al.),U.S. Pat. No. 4,219,625 (Mares et al.), U.S. Pat. No. 5,560,992 (Sargentet al.), and U.S. Pat. No. 5,681,963 (Liss); International PatentPublication Nos. WO 97/22576, WO 97/22659, and WO 97/22660 (E. I. duPont de Nemours and Company); Japanese Patent Publication Nos. 3-041160(Kao Corporation) and 9-323956 (Wako Junyaku Kogyo Co.); andInternational Patent Publication No. WO 99/05345 (Minnesota Mining andManufacturing Company), the descriptions of which are incorporatedherein by reference.

[0056] Of these, particularly preferred are the fluorochemicalgroup-containing derivatives of long-chain (preferably, having at leastabout 30 carbon atoms; more preferably, dimer and trimer, as definedbelow) acids, alcohols, and amines. A preferred class of suchderivatives includes the compounds or mixtures of compounds representedby the formulas:

{(R_(f))_(n)-Q-O—C(O)}_(p)-A

{(R_(f))_(n)-Q-C(O)—O}_(p)-A′

{(R_(f))_(n)-Q-N(R)—C(O)}_(p)-A

{(R_(f))_(n)-Q-C(O)—N(R)}_(p)-A′

[0057] wherein R_(f) is a fluorinated alkyl group (which can optionallycontain one or more catenary (in-chain) heteroatoms such as oxygen)bonded through carbon; n is 1 or 2; Q is a divalent or trivalent linkinggroup or a covalent bond; p is 2 or more, up to the valency of A or A′;R is a hydrogen atom or is a substituted or unsubstituted alkyl group; Ais the residue of a dimer or trimer acid; and A′ is the residue of adimer diol, a dimer diamine, a trimer triol, or a trimer triamine.Preferably, R_(f) is a perfluoroalkyl group having from about 3 to about20 carbon atoms (preferably, from about 4 to about 12 carbon atoms); Ris an alkyl group having from 1 to 6 carbon atoms; Q is—SO₂N(R′)(CH₂)_(k)—, —(CH₂)_(k)—, —CON(R′)(CH₂)_(k)—, or—(CH₂)_(k)SO₂N(R′)(CH₂)_(k)—, where R′ is hydrogen, phenyl, or a shortchain (up to about 6 carbon atoms) alkyl group (preferably, methyl orethyl), and each k is independently an integer from 1 to about 20; A isthe residue of a dimer acid; and A′ is the residue of a dimer diol ordimer diamine. The esters and “reverse” esters are preferred over theamides and “reverse” amides.

[0058] Such fluorochemical group-containing dimer and trimer acid esterscan be prepared by heating a fluorochemical alcohol with either a dimeracid or a trimer acid in the presence of a standard acid catalyst, or byfirst making an acid chloride of the dimer/trimer acid and then reactingthe acid chloride with a fluorochemical alcohol at a slightly elevatedtemperature (for example, 50-60° C.) in the presence of an acidscavenger. Fluorochemical group-containing “reverse” esters can beprepared by reacting a fluorochemical carboxylic acid with a dimer diol,using the same synthetic procedure as described for preparing esters.Fluorochemical group-containing amides can be prepared by reacting afluorochemical amine with a dimer or trimer acid by heating thecomponents together neat at an elevated temperature (at least about 220°C.), or by first making an acid chloride of the dimer/trimer acid andthen reacting the acid chloride with a fluorochemical amine at aslightly elevated temperature. Fluorochemical group-containing “reverse”amides can be prepared by reacting a fluorochemical carboxylic acid witha dimer amine, using the same synthetic procedure as described forpreparing esters.

[0059] The terms “dimer acid” and “trimer acid” refer to oligomerizedunsaturated fatty acid products of relatively high molecular weight. Theproducts are mixtures comprising various ratios of a variety of large orrelatively high molecular weight substituted cyclohexenecarboxylicacids, predominately 36-carbon dibasic acids (dimer acid) and 54-carbontribasic acids (trimer acid), with no single structure sufficient tocharacterize each. Component structures can be acyclic, cyclic(monocyclic or bicyclic), or aromatic.

[0060] Dimer and trimer acids (for use in preparing the above-describedfluorochemical repellents) can be prepared by condensing unsaturatedmonofunctional carboxylic acids such as oleic, linoleic, soya, or talloil acid through their olefinically unsaturated groups, in the presenceof catalysts such as acidic clays. Dimer/trimer acids are commerciallyavailable from a variety of vendors, including Henkel Corporation/EmeryGroup (as EMPol™ 1008, 1061, 1040 and 1043) and Unichema North America(as Pripol™ 1004 and 1009). Dimer diols and diamines can be made fromthe corresponding dimer acid by methods well known in the art. Dimerdiols are commercially available from Henkel Corp./Emery Group as Empol™1070 and 1075 diols. Dimer amines are commercially available from WitcoCorp., for example, as Kemamine™ DP-3695 amine.

[0061] Insulating Materials

[0062] Insulating materials that are suitable for topical treatmentinclude materials that have relatively low surface and bulk conductivityand that are prone to static charge buildup. Such materials include bothsynthetic and naturally-occurring polymers (or the reactive precursorsthereof, for example, mono- or multifunctional monomers or oligomers)that can be either organic or inorganic in nature, as well as ceramics,glasses, and ceramic/polymer composites or ceramers (or the reactiveprecursors thereof).

[0063] Suitable synthetic polymers (which can be either thermoplastic orthermoset) include commodity plastics such as, for example, poly(vinylchloride), polyethylenes (high density, low density, very low density),polypropylene, and polystyrene; engineering plastics such as, forexample, polyesters (including, for example, poly(ethyleneterephthalate) and poly(butylene terephthalate)), polyamides (aliphatic,amorphous, aromatic), polycarbonates (for example, aromaticpolycarbonates such as those derived from bisphenol A),polyoxymethylenes, polyacrylates and polymethacrylates (for example,poly(methyl methacrylate)), some modified polystyrenes (for example,styrene-acrylonitrile (SAN) and acrylonitrile-butadiene-styrene (ABS)copolymers), high-impact polystyrenes (SB), fluoroplastics, and blendssuch as poly(phenylene oxide)-polystyrene and polycarbonate-ABS;high-performance plastics such as, for example, liquid crystallinepolymers (LCPs), polyetherketone (PEEK), polysulfones, polyimides, andpolyetherimides; thermosets such as, for example, alkyd resins, phenolicresins, amino resins (for example, melamine and urea resins), epoxyresins, unsaturated polyesters (including so-called vinyl esters),polyurethanes, allylics (for example, polymers derived fromallyldiglycolcarbonate), fluoroelastomers, and polyacrylates; and thelike and blends thereof. Suitable naturally occurring polymers includeproteinaceous materials such as silk, wool, and leather; and cellulosicmaterials.

[0064] Thermoplastic and thermoset polymers, including those describedabove, are preferred insulating materials, as such polymers can eitherbe topically treated with the antistat/repellent combination or can becombined with it (in bulk) to form a blend. Thermoplastic polymers aremore preferred in view of their melt processability. Preferably, thethermoplastic polymers are melt processable at elevated temperatures,for example, above about 150° C. (more preferably, above about 250° C.;even more preferably, above about 280° C.; most preferably, above about320° C.). Preferred thermoset polymers include polyurethanes, epoxyresins, and unsaturated polyesters. Preferred thermoplastic polymersinclude, for example, polypropylene, polyethylene, copolymers ofethylene and one or more alpha-olefins (for example,poly(ethylene-butene) and poly(ethylene-octene)), polyesters,polyurethanes, polycarbonates, polyetherimides, polyimides,polyetherketones, polysulfones, polystyrenes, ABS copolymers,polyamides, fluoroelastomers, and blends thereof. More preferred arepolypropylene, polyethylene, polyesters, poly(ethylene-octene),polyurethanes, polycarbonates, and blends thereof, with polypropylene,polyethylene, poly(ethylene-octene), polyurethanes, and blends thereofbeing most preferred.

[0065] Preparation and Use of Composition

[0066] Preferably, the composition of the invention can be prepared by(a) combining at least one ionic salt antistat, at least onefluorochemical repellent, and at least one thermoplastic polymer(optionally, along with other additives) and then melt processing theresulting combination; or (b) combining at least one ionic saltantistat, at least one fluorochemical repellent, and at least onethermosetting polymer or ceramer or the reactive precursors thereof(optionally, along with other additives) and then allowing the resultingcombination to cure, optionally with the application of heat or actinicradiation. Alternative processes for preparing the composition include,for example, (c) applying a treatment composition comprising at leastone ionic salt antistat and at least one fluorochemical repellent to atleast a portion of at least one surface of at least one insulatingmaterial; (d) dissolving at least one ionic salt antistat, at least onefluorochemical repellent, and at least one insulating material in atleast one solvent and then casting or coating the resulting solution andallowing evaporation of the solvent, optionally with the application ofheat; and (e) combining at least one ionic salt antistat, at least onefluorochemical repellent, and at least one monomer (optionally, alongwith other additives) and then allowing polymerization of the monomer tooccur, optionally in the presence of at least one solvent and optionallywith the application of heat or actinic radiation. If desired, theantistat and repellent can be utilized separately, for example, one canbe added prior to melt processing, and the other can then be topicallyapplied to the resulting melt-processed combination. Separate topicaltreatments, etc., are also possible.

[0067] To form a melt blend by melt processing, the ionic saltantistat(s) and fluorochemical repellent(s) can be, for example,intimately mixed with pelletized or powdered polymer and then meltprocessed by known methods such as, for example, molding, melt blowing,melt spinning, or melt extrusion. The antistat and repellent additivescan be mixed directly with the polymer or they can be mixed with thepolymer in the form of a “master batch” (concentrate) of the additivesin the polymer. If desired, an organic solution of the additives can bemixed with powdered or pelletized polymer, followed by drying (to removesolvent) and then by melt processing. Alternatively, the additives canbe injected into a molten polymer stream to form a blend immediatelyprior to, for example, extrusion into fibers or films or molding intoarticles.

[0068] After melt processing, an annealing step can be carried out toenhance the development of antistatic and repellent characteristics. Inaddition to, or in lieu of, such an annealing step, the melt processedcombination (for example, in the form of a film or a fiber) can also beembossed between two heated rolls, one or both of which can bepatterned. An annealing step typically is conducted below the melttemperature of the polymer (for example, in the case of polyamide, atabout 150-220° C. for a period of about 30 seconds to about 5 minutes).In some cases, the presence of moisture can improve the effectiveness ofthe ionic salt antistat(s), although the presence of moisture is notnecessary in order for antistatic characteristics to be obtained.

[0069] The ionic salt antistat(s) and fluorochemical repellent(s) can beadded to thermoplastic or thermosetting polymer (or, alternatively, toother insulating material) in amounts sufficient to achieve the desiredantistatic and repellency properties for a particular application. Theamounts can be determined empirically and can be adjusted as necessaryor desired to achieve the antistatic and repellency properties withoutcompromising the properties of the polymer (or other insulatingmaterial). Generally, the ionic salt antistat(s) and the fluorochemicalrepellent(s) can each be added in amounts ranging from about 0.1 toabout 10 percent by weight (preferably, from about 0.5 to about 2percent; more preferably, from about 0.75 to about 1.5 percent) based onthe weight of polymer (or other insulating material).

[0070] In topical treatment of an insulating material, the combinationof ionic salt antistat(s) and fluorochemical repellent(s) can beemployed alone or in the form of aqueous suspensions, emulsions, orsolutions, or as organic solvent (or organic solvent/water) solutions,suspensions, or emulsions. Useful organic solvents include chlorinatedhydrocarbons, alcohols (for example, isopropyl alcohol), esters, ketones(for example, methyl isobutyl ketone), and mixtures thereof. Generally,the solvent solutions can contain from about 0.1 to about 50 percent, oreven up to about 90 percent, by weight non-volatile solids (based on thetotal weight of the components). Aqueous suspensions, emulsions, orsolutions are generally preferred and generally can contain anon-volatile solids content of about 0.1 to about 50 percent,preferably, about 1 to about 10 percent, by weight (based on the totalweight of the components). Alternatively, however, topical treatment canbe carried out by applying (to at least a portion of at least onesurface of at least one insulating material) a topical treatmentcomposition that comprises at least one ionic salt antistat that isliquid at the use or treatment temperature. Such a topical treatmentprocess can involve the use of the neat liquid ionic salt antistat,without added solvent, and is thus preferred from an environmentalperspective over the use of organic solvent solutions of theantistat/repellent combination.

[0071] The topical treatment compositions comprising theantistat/repellent combination can be applied to an insulating materialby standard methods such as, for example, spraying, padding, dipping,roll coating, brushing, or exhaustion (optionally followed by the dryingof the treated material to remove any remaining water or solvent). Thematerial can be in the form of molded or blown articles, sheets, fibers(as such or in aggregated form, for example, yarn, toe, web, or roving,or in the form of fabricated textiles such as carpets), woven andnonwoven fabrics, films, etc. If desired, the antistat/repellentcombination can be co-applied with conventional fiber treating agents,for example, spin finishes or fiber lubricants.

[0072] The topical treatment compositions can be applied in an amountsufficient to achieve the desired antistatic and repellency propertiesfor a particular application. This amount can be determined empiricallyand can be adjusted as necessary or desired to achieve the antistaticand repellency properties without compromising the properties of theinsulating material.

[0073] Any of a wide variety of constructions can be made from thecomposition of the invention, and such constructions will find utilityin any application where some level of antistatic and repellencycharacteristics is required. For example, the composition of theinvention can be used to prepare films and molded or blown articles, aswell as fibers (for example, melt-blown or melt-spun fibers, includingmicrofibers) that can be used to make woven and nonwoven fabrics. Suchfilms, molded or blown articles, fibers, and fabrics exhibit antistaticand water and oil repellency (and soil resistance) characteristics undera variety of environmental conditions and can be used in a variety ofapplications.

[0074] For example, molded articles comprising the composition of theinvention can be prepared by standard methods (for example, by hightemperature injection molding) and are particularly useful as, forexample, headlamp covers for automobiles, lenses (including eyeglasslenses), casings or circuit boards for electronic devices (for example,computers), screens for display devices, windows (for example, aircraftwindows), and the like. Films comprising the composition of theinvention can be made by any of the film making methods commonlyemployed in the art. Such films can be nonporous or porous (the latterincluding films that are mechanically perforated), with the presence anddegree of porosity being selected according to the desired performancecharacteristics. The films can be used as, for example, photographicfilms, transparency films for use with overhead projectors, tapebackings, substrates for coating, and the like.

[0075] Fibers comprising the composition of the invention can be used tomake woven or nonwoven fabrics that can be used, for example, in makingmedical fabrics, medical and industrial apparel, fabrics for use inmaking clothing, home furnishings such as rugs or carpets, and filtermedia such as chemical process filters or respirators. Nonwoven webs orfabrics can be prepared by processes used in the manufacture of eithermelt-blown or spunbonded webs. For example, a process similar to thatdescribed by Wente in “Superfine Thermoplastic Fibers,” Indus. Eng'gChem. 48, 1342 (1956) or by Wente et al. in “Manufacture of SuperfineOrganic Fibers,” Naval Research Laboratories Report No. 4364 (1954) canbe used. Multi-layer constructions made from nonwoven fabrics enjoy wideindustrial and commercial utility, for example, as medical fabrics. Themakeup of the constituent layers of such multi-layer constructions canbe varied according to the desired end-use characteristics, and theconstructions can comprise two or more layers of melt-blown andspunbonded webs in many useful combinations such as those described inU.S. Pat. No. 5,145,727 (Potts et al.) and U.S. Pat. No. 5,149,576(Potts et al.), the descriptions of which are incorporated herein byreference. In multi-layer constructions, the ionic salt antistat(s) andfluorochemical repellent(s) can be used in combination in one or morelayers, or each can be independently segregated in one or more layers.For example, in a spunbonded/melt-blown/spunbonded (“SMS”) three-layerconstruction, the ionic salt antistat(s) can be used in one or bothspunbonded layers, and the fluorochemical repellent(s) can be used inthe melt-blown layer, to impart both antistatic and repellencycharacteristics to the overall construction.

[0076] The ionic salt antistat(s) and fluorochemical repellent(s) usedin the composition of the invention can also find utility as additivesto coatings (for example, polymer or ceramer coatings). Such coatingscan be antistatic, water- and oil-repellent, and scratch-resistant (aswell as soil-resistant) and can be used in the photographic industry oras protective coatings for optical or magnetic recording media.

[0077] If desired, the composition of the invention can further containone or more conventional additives commonly used in the art, forexample, dyes, pigments, antioxidants, ultraviolet stabilizers, flameretardants, surfactants, plasticizers, tackifiers, fillers, and mixturesthereof. In particular, performance enhancers (for example, polymerssuch as polybutylene) can be utilized to improve the antistatic and/orrepellency characteristics in, for example, melt additive polyolefinapplications.

[0078] Objects and advantages of this invention are further illustratedby the following examples, but the particular materials and amountsthereof recited in these examples, as well as other conditions anddetails, should not be construed to unduly limit this invention. In theexamples, where weight percent or parts by weight are indicated, theseare based on the weight of the entire composition unless indicatedotherwise.

EXAMPLES Glossary

[0079] Antistats

[0080] HTS 905 and 905A—Larostat™ HTS 905 or 905A (anhydrous),C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻OSO₂CH₃, available from BASF, Gurnee, Ill.

[0081] HTS-904—3-(2-hydroxyethyl)-1-methyl-2-undecylimidazoliniump-toluenesulfonate, available from BASF, Gurnee, Ill.

[0082] Lithium perfluorobutanesulfonate—available from 3M, St. Paul,Minn.

[0083] Anstex™ SA-300—an antistatic melt additive agent, octadecanoicacid 2-[(2-hydroxyethyl)octadecylamino]ethyl ester, available from TOHOchemical Industry Co., Japan.

[0084] Aluminum Stearate—available from All Chemie Ltd., Mt. Pleasant,S.C.

[0085] Lithium Stearate—available from ACROS Organics USA, Pittsburg,Pa.

[0086] Glycerol Monostearate—available from Sigma-Aldrich, Milwaukee,Wis.

[0087] Aliquat™ 336—Methyltrioctylammonium chloride, available fromSigma-Aldrich, Milwaukee, Wis., or from Henkel Corp., Ambler, Pa.

[0088] Starting Materials for Antistats

[0089] HQ-115—LiN(SO₂CF₃)₂ available from 3M, St. Paul, Minn.

[0090] PBSF—Perfluorobutanesulfonyl fluoride, available fromSigma-Aldrich, Milwaukee, Wis.

[0091] Lithium triflate—Lithium trifluoromethanesulfonate, availablefrom Sigma-Aldrich, Milwaukee, Wis.

[0092] FC-24—Trifluoromethanesulfonic acid, available from 3M, St. Paul,Minn.

[0093] FC-754—Trimethyl-3-perfluorooctylsulfonamidopropylammoniumchloride, available from 3M, St. Paul, Minn.

[0094] FC-94—Lithium perfluorooctanesulfonate, available from 3M, St.Paul, Minn.

[0095] Cetylpyridinium chloride monohydrate—1-Hexadecylpyridiniumchloride, available from Research Organics, Cleveland, Ohio.

[0096] 1,3-Ethylmethylimidazolium chloride—Available from Sigma-Aldrich,Milwaukee, Wis.

[0097] Silver triflate—Silver trifluoromethanesulfonate, available fromSigma-Aldrich, Milwaukee, Wis.

[0098] AgBF₄—Silver tetrafluoroborate, available from Sigma-Aldrich,Milwaukee, Wis.

[0099] NH₄PF₆—Ammonium hexafluorophosphate, available fromSigma-Aldrich, Milwaukee, Wis.

[0100] Acetylcholine chloride—CH₃CO₂CH₂CH₂N(CH₃)₃Cl, available fromResearch Organics, Cleveland, Ohio.

[0101] Choline chloride—HOCH₂CH₂N(CH₃)₃Cl, available from Sigma-Aldrich,Milwaukee, Wis.

[0102] Fluorochemical Repellents

[0103] FC-808—A fluorochemical emulsion of a polymeric fluoroaliphaticester (80 weight percent in water) for fluid repellency, available from3M, St. Paul, Minn.

[0104] Starting Materials for Fluorochemical Repellents

[0105] MeFOSE alcohol—C₈F₁₇SO₂N(CH₃)CH₂CH₂OH, having an equivalentweight of 540, made in two stages by reacting POSFperfluorooctanesulfonyl fluoride with methylamine andethylenechlorohydrin, using a procedure similar to that described inExample 1 of U.S. Pat. No. 2,803,656 (Ahlbrecht et al.).

[0106] Empol™ 1008 acid—a distilled and hydrogenated dimer acid based onoleic acid, having an acid equivalent weight of 305 as determined bytitration, commercially available from Henkel Corp./Emery Group,Cincinnati, Ohio.

[0107] Pripol™ 1048 acid—a hydrogenated distilled dimer/trimer acidbased on oleic acid, commercially available from Unichema North America,Chicago, Ill.

[0108] Thermoplastic Polymers

[0109] PP3505—ESCORENE™ PP3505 polypropylene, having a 400 melt indexflow rate, available from Exxon Chemical Co., Baytown, Tex.

[0110] Montell H422PP—a granular polypropylene polymer (with peroxide)having an 850 melt flow index, available from Montell North America,Wilmington, Del.

[0111] PB0200—polybutylene, available from Shell Chemical Co., Houston,Tex.

[0112] PB8340—copolymer of 1-butene and ethylene, available from ShellChemical Co., Houston, Tex.

[0113] PE6806—ASPUN™ 6806 polyethylene, having a melt flow index of 105g/10 min (as measured by Test Method ASTM D-1238) and having a peakmelting point of 124.8° C., available from Dow Chemical Co., Midland,Mich.

[0114] PS440-200—MORTHANE™ PS440-200 urethane, available from MortonThiokol Corp., Chicago, Ill.

Test Methods

[0115] Test Method I—Melting Point Determination

[0116] The melting points of salts were determined by differentialscanning calorimetry (DSC) using a 20° C. per minute temperature ramp.The peak maximum of the melt transition was taken as the melting point(Tm). Where multiple melt transitions were observed, the peak associatedwith the largest area melt transition was taken as the melting point.

[0117] Test Method II—Onset of Thermal Decomposition Determination

[0118] The onset of thermal decomposition of each salt was determined bythermal gravimetric analysis (TGA) under an inert nitrogen atmosphereusing a 10° C. per minute temperature ramp. The value of the onsettemperature was determined by finding the intersection of theextrapolated tangent at the baseline preceding onset and theextrapolated tangent at the inflection point associated with the stepchange in sample weight.

[0119] Test Method III—Static Charge Dissipation Test

[0120] The static charge dissipation characteristics of nonwovenfabrics, films, and molded sheets were determined with this method. Thetest materials were cut into 9 cm by 12 cm samples and conditioned atrelative humidities (RH) of about 10 percent, 25 percent, and 50 percentfor at least 12 hours. The materials were tested at temperatures thatranged from 22-25° C. The static charge dissipation time was measuredaccording to Federal Test Method Standard 10113, Method 4046,“Antistatic Properties of Materials”, using an ETS Model 406C StaticDecay Test Unit (manufactured by Electro-Tech Systems, Inc., Glenside,Pa.). This apparatus induces an initial static charge (Average InducedElectrostatic Charge) on the surface of the flat test material by usinghigh voltage (5000 volts), and a fieldmeter allows observation of thedecay time of the surface voltage from 5000 volts (or whatever theinduced electrostatic charge was) to 10 percent of the initial inducedcharge. This is the static charge dissipation time. The lower the staticcharge dissipation time, the better the antistatic properties are of thetest material. All reported values of the static charge dissipationtimes in this invention are averages (Average Static Decay Rate) over atleast 3 separate determinations. Values reported as >10, >60, or >100seconds indicate that the material tested has an initial static chargewhich cannot be removed by surface conduction and is not antistatic.When the material tested did not accept a charge of about 3000 volts ormore, it was not considered to have charged sufficiently to beantistatic.

[0121] Test Method IV—Surface Resistivity Test

[0122] This test was conducted according to the procedure of ASTMStandard D-257, “D.C. Resistance or Conductance of InsulatingMaterials”. The surface resistivity was measured under the conditions ofthis test method using an ETS Model 872 Wide Range Resistance Meterfitted with a Model 803B probe (Electro-Tech Systems, Inc., Glenside,Pa.). This apparatus applies an external voltage of 100 volts across twoconcentric ring electrodes contacting the flat test material, andprovides surface resistivity readings in ohm/square units.

[0123] Test Method V—Water Repellency Test

[0124] Nonwoven web samples were evaluated for water repellency using 3MWater Repellency Test V for Floorcoverings (February 1994), availablefrom 3M Company. In this test, samples are challenged to penetrations byblends of deionized water and isopropyl alcohol (IPA). Each blend isassigned a rating number as shown below: Water Repellency Water/IPARating Number Blend (% by volume) 0 100% water 1 90/10 water/EPA 2 80/20water/IPA 3 70/30 water/IPA 4 60/40 water/IPA 5 50/50 water/IPA 6 40/60water/IPA 7 30/70 water/IPA 8 20/80 water/IPA 9 10/90 water/IPA 10 100%IPA

[0125] In running the Water Repellency Test, a nonwoven web or filmsample is placed on a flat, horizontal surface. Five small drops ofwater or a water/IPA mixture are gently placed at points at least twoinches apart on the sample. If, after observing for ten seconds at a 45°angle, four of the five drops are visible as a sphere or a hemisphere,the nonwoven web or film sample is deemed to pass the test. The reportedwater repellency rating corresponds to the highest numbered water orwater/IPA mixture for which the nonwoven sample passes the describedtest.

[0126] It is desirable to have a water repellency rating of at least 4,preferably at least 6.

[0127] Test Method VI—Oil Repellency Test

[0128] Nonwoven web or film samples were evaluated for oil repellencyusing 3M Oil Repellency Test III (February 1994), available from 3MCompany, St. Paul, Minn. In this test, samples are challenged topenetration or droplet spread by oil or oil mixtures of varying surfacetensions. Oils and oil mixtures are given a rating corresponding to thefollowing: Oil Repellency Oil Rating Number Composition 0 (failsKaydol ™ mineral oil) 1 Kaydol ™ mineral oil 2 65/35 (vol) mineraloil/n-hexadecane 3 n-hexadecane 4 n-tetradecane 5 n-dodecane 6 n-decane7 n-octane 8 n-heptane

[0129] The Oil Repellency Test is run in the same manner as is the WaterRepellency Test, with the reported oil repellency rating correspondingto the highest oil or oil mixture for which the nonwoven web or filmsample passes the test.

[0130] It is desirable to have an oil repellency rating of at least 1,preferably at least 3.

Preparation and Characterization of Antistats for Melting Point andThermal Decomposition Antistat 1

[0131] Synthesis of Triethylammonium bis(perfluoroethanesulfonyl)imide,Et₃N⁺H ⁻N(SO₂C₂F₅)₂

[0132] This compound was prepared essentially according to the methoddescribed in U.S Pat. No. 5,874,616 (Howells, et al), Example 3, exceptthat the procedure was terminated once the methylene chloride solventwas evaporated. The resulting product was characterized for meltingpoint (T_(m)) according to Test Method I and for onset of thermaldecomposition (T_(d)) according to Test Method II. Results are shown inTable 1.

Antistat 2

[0133] Synthesis of Tetraethylammonium Trifluoromethanesulfonate, CF₃SO₃³¹ ⁺NEt₄

[0134] In a 2L flask, 300 g of CF₃SO₃H (FC-24) was charged. The acid wasneutralized by slow addition of about 800 g Et4NOH aqueous solution(35%) until the pH reached about 6. A white solid (560 g) was obtainedafter drying by rotary evaporation, then under high vacuum. The solidwas re-crystallized from chloroform-heptane to give 520 g pure product.This product was also characterized for melting point (T_(m)) accordingto Test Method I and for onset of thermal decomposition (T_(d))according to Test Method II. Results are shown in Table 1.

Antistat 3

[0135] Synthesis of Tetraethylammoniumbis(trifluoromethanesulfonyl)imide, (CF₃SO₂)₂N⁻ ⁺NEt₄ in Water-CH₂Cl₂Mixed Solvent

[0136] In a 1L flask, 50 g of (CF₃SO₂)₂N⁻ Li⁺ (HQ-115) was dissolved in50 g of deionized water. The solution was combined with 89 g of 35%Et₄NOH aqueous solution under N₂. Solid precipitated during theaddition, which was dissolved by the addition of 50 g CH₂Cl₂. The bottomorganic layer was isolated. The aqueous solution was extracted withanother 50 g of CH₂Cl₂. The combined organic solution was washed withwater (2×25 mL), and volatiles were removed by rotary evaporation.Re-crystallization of the crude product from CH₃OH—H₂O gave 70 g ofwhite solid after full vacuum drying. The product was characterized formelting point (T_(m)) according to Test Method I and for onset ofthermal decomposition (T_(d)) according to Test Method II. Results areshown in Table 1.

Antistat 4

[0137] Synthesis of Tetrabutylammoniumbis(trifluoromethanesulfonyl)imide, (C₄H₉)₄N⁺ ⁻N(SO₂CF₃)₂

[0138] This compound was prepared by reacting (C₄H₉)₄N⁺Br⁻(Sigma-Aldrich, Milwaukee, Wis.) with approximately a 10% molar excessof Li⁺ ⁻N(SO₂CF₃)₂ (HQ-115) essentially according to the proceduredescribed in Example 18 of U.S. Pat. No. 5,554,664 (Lamanna et al). Theresulting product was characterized for melting point (T_(m)) accordingto Test Method I and for onset of thermal decomposition (T_(d))according to Test Method II. Results are shown in Table 1. TABLE 1Melting Point (T_(m)) and Onset of Thermal Decomposition (T_(d)) ValuesT_(m) T_(d) Antistat Formula (° C.) (° C.) 1 Et₃N⁺H ⁻N(SO₂C₂F₅)₂ −10 3512 CF₃SO₃ ⁻ ⁺NEt₄ 133 371 3 (CF₃SO₂)₂N⁻ ⁺NEt₄ 8 426 4 (C₄H₉)₄N⁺⁻N(SO₂CF₃)₂ 93 401 23 (C₈H₁₇)₃N⁺(CH₃) Cl⁻ <28 177

[0139] The data in Table 1 shows that Antistats 1-4, which compriseweakly coordinating fluoroorganic anions, exhibited much greater thermalstability than Antistat 23, which has the more strongly coordinatingchloride anion.

Antistat 5

[0140] Synthesis of 1-HexadecylpyridiniumBis(perfluoroethanesulfonyl)imide, n-C₁₆H₃₃-cyc-N⁺C₅H₅ ⁻N(SO₂C₂F₅)₂

[0141] This compound was prepared essentially according to the method ofAntistat 6, except that 85.1 g of Li⁺ ⁻N(SO₂C₂F₅)₂ (HQ-115) was employedas the anion precursor instead of Li⁺ ⁻OSO₂C₄F₉. The product wascharacterized for melting point (T_(m)) according to Test Method I andfor onset of thermal decomposition (T_(d)) according to Test Method II.Results are shown in Table 2.

Antistat 6

[0142] Synthesis of 1-Hexadecylpyridinium Perfluorobutanesulfonate,n-C₁₆H₃₃-cyc-N⁺C₅H₅ ⁻OSO₂C₄F₉

[0143] Cetylpyridinium chloride monohydrate (75 g) was dissolved in 800ml water with gentle heating and magnetic stirring. To this solution wasadded 67.3 g of Li⁺⁻ OSO₂C₄F₉ (prepared by hydrolysis of C₄F₉SO₂F [PBSF]with LiOH) dissolved in 600 mL of water with stirring. The resultingproduct precipitated immediately and was isolated by suction filtration.The product was washed with copious amounts of water and then driedinitially by suction and then in vacuo at 10⁻² Torr, 40° C. The productwas characterized for melting point (T_(m)) according to Test Method Iand for onset of thermal decomposition (T_(d)) according to Test MethodII. Results are shown in Table 2.

Antistat 7

[0144] Synthesis of 1-Hexadecylpyridinium Perfluorooctanesulfonate,n-C₁₆H₃₃-cyc-N⁺C₅H₅ ⁻OSO₂C₈F₁₇

[0145] This compound was prepared essentially according to the method ofAntistat 6, except that 111.3 g of Li⁺ ⁻OSO₂C₈F₁₇ (FC-94) was employedas the anion precursor. The resulting product was characterized formelting point (T_(m)) according to Test Method I and for onset ofthermal decomposition (T_(d)) according to Test Method II. Results areshown in Table 2.

Antistat 8

[0146] Synthesis of n-ButylpyridiniumBis(trifluoromethanesulfonyl)imide, n-C₄H₉-cyc-N⁺C₅H₅ ⁻N(SO₂CF₃)₂

[0147] A solution of 50 g Li⁺ ⁻N(SO₂CF₃)₂ (HQ-115) (287 g/mol, 0.174mol) and 100 ml DI water was prepared. Another solution of 30 gbutylpyridinium chloride (171.6 g/mol, 0.174) and 100 ml deionized waterwas prepared. The two solutions were added to a separatory funnel alongwith 200 ml methylene chloride. The mixture was thoroughly shaken, andthe phases were allowed to separate. The organic phase was isolated andwashed with 3×200 ml deionized water. The organic layer was thenconcentrated by reduced pressure distillation on a rotary evaporator.The resulting yellow oil was vacuum dried at 120 C. overnight to afford70 g product (97% yield). The product was characterized for meltingpoint (T_(m)) according to Test Method I and for onset of thermaldecomposition (T_(d)) according to Test Method II. Results are shown inTable 2.

Antistat 9

[0148] Synthesis of n-Butylpyridinium Perfluorobutanesulfonate,n-C₄H₉-cyc-N⁺C₅H₅ ⁻OSO₂C₄F₉

[0149] A solution of 20 g butylpyridinium chloride (171.6 g/mol, 0.116mol) was made with 100 ml deionized water. A similar solution wasprepared using 35.7 g Li⁺⁻OSO₂C₄F₉ (prepared by hydrolysis of C₄F₉SO₂F[PBSF] with LiOH) (306 g/mol, 0.116 mol) and 100 ml water. The twosolutions were added to a separatory funnel along with 200 ml methylenechloride. The mixture was thoroughly shaken, and the phases were allowedto separate. The organic phase was isolated and washed with 200 ml DIwater. The mixture was slow to separate, consequently further washingswere not done. The organic layer was concentrated by reduced pressuredistillation on a rotary evaporator, and then dried under vacuum at 130°C. overnight. The resulting yellow oil weighed 44 g (87% yield) and wascharacterized for melting point (T_(m)) according to Test Method I andfor onset of thermal decomposition (T_(d)) according to Test Method II.Results are shown in Table 2. TABLE 2 Melting Point (T_(m)) and Onset ofThermal Decomposition (T_(d)) Values T_(m) T_(d) Antistat Formula (° C.)(° C.) 5 n-C₁₆H₃₃-cyc-N⁺C₅H₅ ⁻N(SO₂C₂F₅)₂ 34 396 6 n-C₁₆H₃₃-cyc-N⁺C₅H₅⁻OSO₂C₄F₉ 95 357 7 n-C₁₆H₃₃-cyc-N⁺C₅H₅ ⁻OSC₂C₈F₁₇ 93 364 8n-C₄H₉-cyc-N⁺C₅H₅ ⁻N(SO₂CF₃)₂ 33 430 9 n-C₄H₉-cyc-C₅H₅ ⁻OSO₂C₄F₉ 63 391

[0150] Table 2 shows that the pyridinium cation-containing Antistats5-9, which comprise weakly coordinating fluoroorganic anions, exhibitedvery good thermal stability.

Antistat 10

[0151] Synthesis of 1,3-EthylmethylimidazoliumBis(trifluoromethanesulfonyl)imide, CH₃-cyc-(N⁺C₂H₂NCH)CH₂CH₃⁻N(SO₂CF₃)₂

[0152] 1,3-Ethylmethylimidazolium chloride (50.0 g) and LiN(SO₂CF₃)₂(HQ-115) (102.8 g) were combined in 500 mL of water with magneticstirring. An immiscible light yellow oil of low viscosity separated as alower liquid phase. The mixture was transferred to a separatory funnel,and 500 mL of methylene chloride was added. The mixture was shakenvigorously and allowed to phase separate. The lower organic phase wasisolated and washed with two additional 500 mL portions of water. Thewashed methylene chloride phase was isolated, dried over anhydrousaluminum oxide beads, filtered by suction and vacuum stripped at 30-100°C., 20-10⁻³ Torr to remove all volatiles. A total of 112.2 g (84% yield)of light yellow oil of high purity was obtained, which was identified asthe title compound by ¹H and ¹⁹F NMR. The product was also characterizedfor melting point (T_(m)) according to Test Method I and for onset ofthermal decomposition (T_(d)) according to Test Method II. Results areshown in Table 3.

Antistat 11

[0153] Synthesis of 1,3-EthylmethylimidazoliumNonafluorobutanesulfonate, CH₃-cyc-(N⁺C₂H₂NCH)CH₂CH₃ ⁻OSO₂C₄F₉

[0154] 1,3-Ethylmethylimidazolium chloride (49.1 g) and LiOSO₂C₄F₉(107.6 g, prepared by hydrolysis of C₄F₉SO₂F with LiOH) were combined in500 mL of water with magnetic stirring. A homogeneous aqueous solutionwas formed, which was transferred to a separatory funnel, combined with500 mL of CH₂Cl₂ and worked up essentially according to the procedurefor Antistat 10. After vacuum stripping all volatiles, a total of 65.0 g(47% yield) of light yellow oil of high purity was obtained, which wasidentified as the title compound by ¹H and ¹⁹F NMR. The product was alsocharacterized for melting point (T_(m)) according to Test Method I andfor onset of thermal decomposition (T_(d)) according to Test Method II.Results are shown in Table 3.

Antistat 12

[0155] Synthesis of 1,3-Ethylmethylimidazoliumtrifluoromethanesulfonate, CH₃-cyc-(N⁺C₂H₂NCH)CH₂CH₃ ⁻OSO₂CF₃

[0156] 1,3-Ethylmethylimidazolium chloride (29 g, 0.199 mole) wasdissolved in 100 ml of water and added to solution of 50 g silvertriflate (0.195 mol) in 200 g water with stirring. The resulting silverchloride precipitate was removed by filtration, and the solids werewashed with 100 ml of deionized water. The filtrate was concentrated ona rotary evaporator and further dried at 75° C. overnight to provide47.5 g of a light green oil that was characterized by ¹H and ¹⁹F NMR.The product was also characterized for melting point (T_(m)) accordingto Test Method I and for onset of thermal decomposition (T_(d))according to Test Method II. Results are shown in Table 3.

Antistat 13

[0157] Synthesis of 1,3-Ethylmethylimidazolium Tetrafluoroborate,CH₃-cyc-(N⁺C₂H₂NCH)CH₂CH₃ BF₄ ⁻

[0158] Separate solutions of 49.6 g AgBF4 (194.68 g/mol, 0.255 mol) in200 ml distilled water, and 37.35 g 1,3-ethylmethylimidazolium chloride(146.62 g/mol, 0.255 mol) in 200 ml distilled water were prepared. Thetwo solutions were mixed together, instantly forming a whiteprecipitate. The precipitate was allowed to settle, followed byfiltration through a D-frit. The filtrate was concentrated, but not todryness, and allowed to stand at room temperature overnight. The nextmorning a black precipitate was observed to have fallen out of solution.The solution was passed through filter paper to removed the small amountof solid. The remaining water was removed by reduced pressuredistillation on a rotary evaporator. The remaining oil was dissolved in200 ml acetonitrile. More insoluble black precipitate was formed and wasfiltered out of the solution. The resulting yellow filtrate wasconcentrated on the rotary evaporator, and the resulting oil was driedovernight under vacuum at 75 C. The isolated weight of product was 40 g(79% yield). The product was characterized for melting point (T_(m))according to Test Method I and for onset of thermal decomposition(T_(d)) according to Test Method II. Results are shown in Table 3.

Antistat 14

[0159] Synthesis of 1,3-Ethylmethylimidazolium Hexafluorophosphate,CH₃-cyc-(N⁺C₂H₂NCH)CH₂CH₃ PF₆ ⁻

[0160] A solution of 500 ml acetonitrile and 73.1 g1,3-ethylmethylimidazolium chloride (146.6 g/mol, 0.498 mol) wasprepared in a 1L flask. Another solution of 250 ml acetonitrile and 81.1g NH₄PF₆ (163 g/mol, 0.498 mol) was similarly prepared and added to theformer solution. A white precipitate instantly formed on mixing of thetwo solutions. The flask was chilled to near 0° C. for 1 hour followedby filtration through high purity Celite™ filter agent using a D-frit.The solvent was removed from the filtrate by reduced pressuredistillation on a rotary evaporator. The resulting ionic salt was driedunder vacuum at 75 C. overnight. The isolated weight of the ionic saltproduct was 114 g (89% yield). The product was characterized for meltingpoint (T_(m)) according to Test Method I and for onset of thermaldecomposition (T_(d)) according to Test Method II. Results are shown inTable 3. TABLE 3 Melting point (T_(m)) and Onset of ThermalDecomposition (T_(d)) Values T_(m) T_(d) Antistat Formula (° C.) (° C.)10 CH₃-cyc-(N⁺C₂H₂NCH)CH₂CH₃ ⁻N(SO₂CF₃)₂ −18 450 11CH₃-cyc-(N⁺C₂H₂NCH)CH₂CH₃ ⁻OSO₂C₄F₉ 18 410 12 CH₃-cyc-(N⁺C₂H₂NCH)CH₂CH₃⁻OSO₂CF₃ −16 429 13 CH₃-cyc-(N⁺C₂H₂NCH)CH₂CH₃ BF₄ ⁻ 7 420 14CH₃-cyc-(N⁺C₂H₂NCH)CH₂CH₃ PF₆ ⁻ 70 490

[0161] The data of Table 3 show that the imidazolium cation-containingantistats, which comprise weakly coordinating fluoroorganic anions, allexhibited excellent thermal stability, with all Td values greater than400° C.

Antistat 15

[0162] Synthesis of 1-Dodecyl-2-ethyl-3-[2-hydroxyethyl]imidazoliniumToluenesulfonate, C₁₂H₂₅-cyc-[N⁺C₂H₄N(CH₂CH₂OH)C]C₂H₅ ⁻OSO₂C₆H₄CH₃

[0163] A 142.2 g sample of 2-ethyl-3-[2-hydroxyethyl]imidazoline(prepared essentially as described in U.S. Pat. No. 4,014,880) wascombined with 340 g of 1-dodecyl toluenesulfonate (prepared essentiallyas described in Organic Synthesis, Collected Volume 3, p. 336 (1955) ina 1 liter three-neck round bottom flask and heated at a temperature of75° C. with stirring for 4 hours. The resulting imidazolinium salt wastransferred to a container for storage.

Antistat 16

[0164] Synthesis of Octyldimethyl-2-hydroxyethylammoniumbis(trifluoromethylsulfonyl)imide, C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻N(SO₂CF₃)₂

[0165] A 19.2 g sample of C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻OSO₂CH₃ (HTS 905A) wascombined with 15.7 g LiN(SO₂CF₃)₂ (HQ-115) in 120 mL of water. Afteragitating the mixture, a clear, immiscible oil separated as a lowerliquid phase. The mixture was transferred to a separatory funnel and 125mL of methylene chloride was added. The mixture was shaken vigorouslyand allowed to phase separate. The lower organic phase was isolated andwashed with two additional 125 mL portions of water. The washedmethylene chloride phase was isolated, dried over anhydrous aluminumoxide beads, filtered by suction and vacuum stripped at 30-100° C.,20-10⁻³ Torr to remove all volatiles. A colorless oil (22.6 g, 85%yield) of high purity was obtained, which was identified as the titlecompound by ¹H, ¹³C and ¹⁹F NMR. The product was also characterized formelting point (T_(m)) according to Test Method I and for onset ofthermal decomposition (T_(d)) according to Test Method II. Results areshown in Table 4.

Antistat 17

[0166] Synthesis of Octyldimethyl-2-hydroxyethylammoniumperfluorobutanesulfonate, C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻OSO₂C₄F₉

[0167] A 118.5 g (0.399 mol) sample of C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻OSO₂CH₃(HTS 905A) was dissolved in about 250 ml of water and 123.9 g (0.399mol) of LiOSO₂C₄F₉ (prepared by hydrolysis of C₄F₉SO₂F [PBSF] with LiOH)was dissolved in about 100 ml of water. The two solutions were added toa separatory funnel and the mixture was shaken vigorously. Next 200 mlof methylene chloride was added to the funnel and the contents wereshaken and allowed to phase separate. The lower methylene chloride layerwas washed twice with about 200 ml of water and concentrated on a rotaryevaporator at about 85° C. for about 45 minutes to yield an off-whitesolid product, which was characterized by ¹H and ¹³C nuclear magneticresonance spectroscopy (NMR). The product was also characterized formelting point (T_(m)) according to Test Method I and for onset ofthermal decomposition (T_(d)) according to Test Method II. Results areshown in Table 4.

Antistat 18

[0168] Synthesis of Octyldimethyl-2-hydroxyethylammoniumtrifluoromethanesulfonate, C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻OSO₂CF₃

[0169] Into 30 g of acetonitrile in a 125 ml Erlenmeyer flask wasdissolved with heating 29.7 g (0.1 mole) HTS-905A (C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH^(−O) ₃SCH₃) and then cooled in an ice bath for 10 minutes. In another125 ml Erlenmeyer flask was dissolved with heating 15.6 g (0.1 mole)lithium triflate into 30 ml of acetonitrile. Next, the lithium triflatesolution was added over a period of about 1 minute to the stirred,cooled HTS-905A solution with generation of a white precipitate. About 2ml of acetonitrile was used to rinse the Erlenmeyer flask that held thelithium triflate solution, and this was also added to the HTS-905Asolution. The resulting reaction mixture was allowed to stir for about10 minutes and was then vacuum filtered through a pad of Celite™ filteragent on a 125 ml Buchner funnel with a C porosity frit. The reactionflask and Celite™ pad were washed with an additional 30 g of ice-coldacetonitrile. The filtrate was concentrated on a rotary evaporator atabout 50 mm Hg with a bath temperature of about 85° C. for about 45minutes to yield 24.5 g of a clear solid product, which wascharacterized by ¹H and ¹³C NMR. The product was also characterized formelting point (T_(m)) according to Test Method I and for onset ofthermal decomposition (T_(d)) according to Test Method II. Results areshown in Table 4.

Antistat 19

[0170] Synthesis of Octyldimethyl-2-hydroxyethylammoniumtris(trifluoromethanesulfonyl)methide, C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻C(SO₂CF₃)₃

[0171] A 20.0 g sample of C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻OSO₂CH₃ (HTS 905) wascombined with 29.6 g HC(SO₂CF₃)₃ (prepared as described in Example 1 ofU.S. Pat. No. 5,554,664 (Lamanna et al.) in 250 mL of water. Afteragitating the resulting mixture, a clear, viscous, pale yellow,immiscible oil separated as a lower liquid phase. The mixture wastransferred to a separatory funnel, combined with 300 mL of methylenechloride, and worked up essentially according to the procedure Antistat16. After vacuum stripping all volatiles, a total of 29.0 g (79% yield)of pale yellow oil product was obtained, which was identified as thetitle compound by ¹H and 19F NMR. Estimated purity from the NMR analysiswas greater than 90 weight %, the major impurity being the corresponding⁻C(SO₂CF₃)₂(SO₂F) salt. The product was also characterized for meltingpoint (T_(m)) according to Test Method I and for onset of thermaldecomposition (T_(d)) according to Test Method II. Results are shown inTable 4.

Antistat 20

[0172] Synthesis of Trimethyl-2-acetoxyethylammoniumbis(trifluoromethylsulfonyl)imide, (CH₃)₃N⁺CH₂CH₂OC(O)CH₃ ⁻N(SO₂CF₃)₂

[0173] Acetylcholine chloride (98 g, Research Organics, Cleveland, Ohio)and LiN(SO₂CF₃)₂ (HQ-115) (165.8 g) were combined in 600 mL of waterwith magnetic stirring. A viscous, immiscible oil separated as a lowerliquid phase. The resulting mixture was worked up essentially asdescribed for Antistat 16, except that the ionic liquid product was notcompletely miscible with methylene chloride, forming 3 separate liquidphases in the presence of water. The lower ionic liquid phase and themiddle CH₂Cl₂ phase were both carried through the workup. After vacuumstripping all volatiles, a total of 179.1 g (77% yield) of colorless oilproduct of high purity was obtained, which was identified as the titlecompound by ¹H, ¹³C and ¹⁹F NMR. The product was also characterized formelting point (T_(m)) according to Test Method I and for onset ofthermal decomposition (T_(d)) according to Test Method II. Results areshown in Table 4.

Antistat 21

[0174] Synthesis of Trimethyl-2-hydroxyethylammoniumbis(perfluorobutanesulfonyl)imide, (CH₃)₃N⁺CH₂CH₂OH ⁻N(SO₂C₄F₉)₂

[0175] Choline chloride (37.34 g) and LiN(SO₂C₄F₉)₂ (142.7 g, preparedessentially according to Example 4 in U.S. Pat. No. 5,874,616 (Howellset al.) were combined in 400 mL of water with magnetic stirring. Aviscous, immiscible oil separated as a lower liquid phase. The mixturewas transferred to a separatory funnel, and 110 mL of diethyl ether wereadded. The mixture was shaken vigorously and allowed to phase separate.The lower organic phase was isolated and washed with two additional 400mL portions of water. The washed ether phase was isolated and vacuumstripped at 30-100° C., 20-10⁻³ Torr to remove all volatiles. Theresulting colorless oil product (155.3 g, 93% yield) of high purity wasobtained, which was identified as the title compound by ¹H, ¹³C and ¹⁹FNMR. The product was also characterized for melting point (T_(m))according to Test Method I and for onset of thermal decomposition(T_(d)) according to Test Method II. Results are shown in Table 4.

Antistat 22

[0176] Larostat™ HTS 905A, octyldimethylhydroxyethylammoniummethanesulfonate (C₈H₁₇N⁺(CH₃)₂C₂H₄OH ⁻OSO₂CH₃) was also characterizedfor melting point (T_(m)) according to Test Method I and for onset ofthermal decomposition (T_(d)) according to Test Method II. Results areshown in Table 4. TABLE 4 Melting Point (T_(m)) and Onset of ThermalDecomposition (T_(d)) Values Anti- T_(m) T_(d) stat Formula (° C.) (°C.) 16 C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻N(SO₂CF₃)₂ None 409 detected 17C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻OSO₂C₄F₉ 147 374 18 C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH⁻OSO₂CF₃ −26 370 19 C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻C(SO₂CF₃)₃ None 387 detected20 (CH₃)₃N⁺CH₂CH₂OC(O)CH3 ⁻N(SO₂CF₃)₂ 24 361 21 (CH₃)₃N⁺CH₂CH₂OH⁻N(SO₂C₄F₉)₂ 32 402 22 C₈H₁₇N⁺(CH₃)₂CH₂CH₂OH ⁻OSO₂CH₃ About 30 289

[0177] The results in Table 4 show that among antistats having the samecation, those containing weakly coordinating fluoroorganic anions(Antistats 16-21) exhibited greatly increased thermal stability relativeto that of Antistat 22, which has a more strongly coordinating anion.

Antistat 23

[0178] Aliquat™ 336, methyltrioctylammonium chloride ((C₈H₁₇)₃N⁺(CH₃)Cl⁻), a liquid at room temperature, was characterized for onset ofthermal decomposition (T_(d)) according to Test Method II. Results areshown in Table 1.

Antistat 24

[0179] Synthesis of tetrabutylphosphonium perfluorobutanesulfonate,(C₄H₉)₄P⁺ ⁻OSO₂C₄F₉

[0180] This compound can be prepared as follows: Potassiumperfluorobutanesulfonate is prepared essentially as in Example 3 of U.S.Pat. No. 2,732,398 (Brice et al.), except that PBSF is substituted forCF₃(CF₂)₄SO₂F. The potassium ion is exchanged for a proton using an ionexchange column (Amberjet™ 1200 H, available from Sigma-Aldrich,Milwaukee, Wis.). The resulting perfluorobutanesulfonic acid is combinedwith an equal molar amount of tetrabutylphosphonium hydroxide (availablefrom Sigma-Aldrich, Milwaukee, Wis.) in an acid-base reaction, resultingin a high yield and high purity tetrabutylphosphoniumperfluorobutanesulfonate.

Preparation of Repellent Additives

[0181] Fluorochemical Repellent FR-1

[0182] Fluorochemical Repellent FR-1 (a fluorochemical oxazolidinone)was prepared by reacting N-methylperfluorooctylsulfonamide withepichlorohydrin to form the fluorochemical chlorohydrin,C₈F₁₇SO₂N(Me)CH(OH)CH₂Cl, which was further reacted with octadecylisocyanate at a 1:1 molar ratio followed by ring closure usingessentially the same procedure as described in Scheme I of U.S. Pat. No.5,025,052 (Crater et al.).

[0183] Fluorochemical Repellent FR-2

[0184] Fluorochemical Repellent FR-2 (a fluorochemical ester) wasprepared by esterifying MeFOSE alcohol with Empol™ 1008 dimer acid at amolar ratio of 2:1 using the following procedure. A 500 mL 2-neckedround-bottom flask equipped with overhead condenser, thermometer andDean-Stark trap wrapped with heat tape was charged with 57.8 g (0.190eq) of Empol™ 1008 dimer acid, 100 g (0.185 eq) of MeFOSE alcohol, 1 gof p-toluenesulfonic acid and 50 g of toluene. The resulting mixture wasplaced in an oil bath heated to 150° C. The degree of esterification wasmonitored by measuring the amount of water collected in the Dean-Starktrap and also by using gas chromatography to determine the amount ofunreacted fluorochemical alcohol. After 18 hours of reaction, about 2.8mL of water was collected and a negligible amount of fluorochemicalalcohol remained, indicating a complete reaction. The reaction mixturewas then cooled to 100° C. and was twice washed with 120 g aliquots ofdeionized water, the final water wash having a pH of 3. The final washwas removed from the flask by suction, and the reaction mixture washeated to 120° C. at an absolute pressure of about 90 torr to removevolatiles. The resulting product, a brownish solid, was characterized ascontaining the desired fluorochemical ester by ¹H and ¹³C NMRspectroscopy and thermogravimetric analysis.

[0185] Fluorochemical Repellent FR-3

[0186] Fluorochemical Repellent FR-3 (a fluorochemical ester) wasprepared by esterifying MeFOSE alcohol with Pripol™ 1048 dimer/trimeracid at a molar ratio of 2:1 using essentially the same procedure as wasused for preparing Fluorochemical Repellent FR-2.

[0187] Fluorochemical Repellent FR4

[0188] Fluorochemical Repellent FR-4 (a fluorochemical ester) wasprepared by esterifying MeFOSE alcohol with dodecanedioic acid at amolar ratio of 2:1 using essentially the same procedure as was used forpreparing Fluorochemical Repellent FR-2.

Example 1

[0189] Fluorochemical Repellent FR-1 and HTS-905 (Antistat 22) were dryblended with a mixture of polybutylene PB0200 and polypropylene PP3505400 melt flow resin (in a weight ratio of 1 part PB0200 to 10 partsPP3505) at 0.85 and 1 weight % of the polypropylene resin, respectively.The mixture was extruded, on a 1.9 cm Brabender extruder with a 25.4 cmdie, into blown microfibers with a diameter of less than about 10microns (Wente, Van A., “superfine Thermoplastic fibers”, Industrial andEng. Chemistry, Vol. 48, No. 8, 1956, pp. 1342-1345, and Naval ResearchLaboratory Report 111437, Apr. 15, 1954). The first extruder zone wasset at 265° C., and all other zones were set at 275° C. The die airtemperature was set at 277° C., and the melt temperature was recorded at279° C. The metering gear pump speed was set at 70 rpm. The die wasconfigured with an air gap setting of 0.763 mm and a set back of 0.69mm. With a collector distance of 30.5 cm, the take up speed was set todeliver a melt blown nonwoven formed from the microfibers with a basisweight of 50 grams/m². The resulting nonwoven samples were calendered ona 5% bond area embossing roll at 93.3° C. at 30.5 cm/min. and at 35.7Kg/lineal cm. The nonwoven samples were tested for oil and waterrepellency according to Test Methods V and VI. The nonwoven samples werealso conditioned at 50% relative humidity (23° C.) and tested for staticcharge dissipation according to Test Method III. Results are shown inTable 5.

Comparative Example C1

[0190] Nonwoven samples were made and tested essentially as in Example1, except that no HTS-905 was used. The results are shown in Table 5.

Comparative Example C2

[0191] Nonwoven samples were made and tested essentially as in Example1, except that no repellent was used, and the level of HTS-905 was 0.5weight % of the polypropylene resin. The results are shown in Table 5.TABLE 5 Repellency and Static Charge Dissipation Properties ofPolypropylene Melt-Blown Nonwovens Repel- Repel- Static lent Antistatlency Decay Example No. (Wt %) (Wt %) O W (sec) 1 FR-1 Antistat 22 6 100.07 (0.85%) (1%) C1 FR-1 None 6 10 >100.0 (0.85%) C2 None Antistat 22 03 0.01 (1%)

[0192] The results in Table 5 show that the combination of repellent andionic antistat compound in a thermoplastic polymer provided excellentstatic charge dissipation and excellent repellency properties.

Examples 2-6 and Comparative Example C3

[0193] Fluorochemical Repellent FR-1 and Antistat 15C₁₂H₂₅-cyc-[N⁺C₂H₄N(CH₂CH₂OH)C]C₂H₅ ⁻OSO₂C₆H₄CH₃) were dry blended withPP3505. FR-1 was used at 1 weight % based on the weight of PP3505, andAntistat 15 was used at 0.5, 0.6, 0.7, 0.8, and 1 weight %, also basedon the weight of PP3505. Nonwoven samples were made and testedessentially as in Example 1. For comparison purposes, nonwoven sampleswere made and tested essentially as in Example 1 without repellent orantistat (Comparative Example C3). The results are shown in Table 6.

Example 7

[0194] Fluorochemical Repellent FR-1 (1 weight %) and Antistat 15 (1weight %) were dry blended with a mixture of PP3505 (80 weight %) andPB8340 (20 weight %). Nonwoven samples were made and tested essentiallyas in Example 1, and the results are shown in Table 6. TABLE 6Repellency and Static Charge Dissipation Properties of PolypropyleneMelt-Blown Nonwovens Static Repellent FR-1 Antistat 15 Repellency DecayExample No. (weight %) (weight %) Oil Water (sec) C3 0 0 0 2 WNC¹ 2 1.00.5 3 8 0.15 3 1.0 0.6 3 8 0.11 4 1.0 0.7 2 8 0.06 5 1.0 0.8 2 8 0.09 61.0 1.0 2 8 0.04 7 1.0 1.0 4 9 0.05

[0195] The results in Table 6 show that a combination of afluorochemical oxazolidinone and Antistat 15 (imidazoliniumtoluenesulfonate ionic antistat) provided both repellency and goodstatic charge dissipation properties in polypropylene, and that theseproperties were further enhanced with added polybutylene.

Example 8

[0196] Fluorochemical Repellent FR-1 (0.85 weight %) and antistatHTS-904 (1 weight %) were dry blended with PP3505. Nonwoven samples weremade from this blend and tested essentially as in Example 1. The resultsare shown in Table 7.

Example 9

[0197] Fluorochemical Repellent FR-1 (0.85 weight %) and antistatHTS-904 (1 weight %) were dry blended with a mixture of PP3503 (85weight %) and PB8340 (15 weight %). Nonwoven samples were made from thisblend and tested essentially as in Example 1. The results are shown inTable 7. TABLE 7 Repellency and Static Charge Dissipation Properties ofPolypropylene Melt-Blown Nonwovens Repel- Repel- Static Example PB8340lent Antistat lency Decay No. (Wt %) (wt %) (Wt %) O W (sec) 8 0 FR-1HTS-904 2 9 0.01 (0.85%) (1%) 9 15 FR-1 HTS-904 6 10 0.05 (0.85%) (1%)

[0198] The results in Table 7 show that the addition of polybutylenesignificantly increased the repellency of a polypropylene nonwovencontaining a combination of a fluorochemical repellent and an antistat,without loss of excellent antistatic properties.

Comparative Examples C4-C6

[0199] Nonwoven samples containing 0 or 1.0 weight % FluorochemicalRepellent FR-1 and 0, 1.0, or 1.25 weight % Anstex™ SA-300 nonionicantistat were prepared and tested essentially as in Example 1. Theresults are shown in Table 8. TABLE 8 Repellency and Static ChargeDissipation Properties of Polypropylene Melt-Blown Nonwovens AntistatStatic Repellent FR-1 SA-300 Repellency Decay Example No. (wt. %) (wt.%) Oil Water (sec) C3 0 1.0 0 2 14.9 C4 1.0 0.0 4 9 WNC¹ C5 1.0 1.25 4 8WNC¹

[0200] The results in Table 8 show that a loss of antistatic propertieswas obtained when a nonionic antistat was used in combination with arepellent.

Examples 10-19 and Comparative Examples C7-C17

[0201] Antistats 16-19 and 22 along with 1 or 1.25 weight %Fluorochemical Repellent FR-1, FR-2, FR-3, or FR-4 were incorporatedinto polypropylene melt blown fibers, which were processed into nonwovenfabrics according to the melt-blown extrusion procedure described inU.S. Pat. No. 5,300,357 (Gardiner), column 10, the description of whichis incorporated herein by reference. For comparison, polypropylene meltblown fibers without repellent or antistat, and with an Antistat butwithout a repellent were made and formed into nonwoven fabrics byessentially the same process. For additional comparison, polypropylenemelt blown fibers with only Fluorochemical Repellents FR-1, FR-2, FR-3,or FR-4 were made and processed into nonwoven fabrics by essentially thesame process. The extruder used was a Brabender 42 mm conical twin screwextruder, with maximum extrusion temperature of 270-280° C. and distanceto the collector of 12 inches (30 cm).

[0202] Antistat, Fluorochemical Repellent, and Escorene ™ PP3505polypropylene were mixed by blending in a paperboard container using amixer head affixed to a hand drill for about one minute until a visuallyhomogeneous mixture is obtained. The Antistat and FluorochemicalRepellent were dispersed in the molten polypropylene by mixing in themelt extrusion apparatus just prior to melt blowing. Except as noted,the weight percent of the compound in the polypropylene was about 1%.

[0203] The process condition for each mixture was the same, includingthe melt blowing die construction used to blow the microfiber web, thebasis weight of the web (50±5 g/m²) and the diameter of the microfibers(5-18 micrometers). Unless otherwise stated, the extrusion temperaturewas 270-280° C., the primary air temperature was 270° C., the pressurewas 124 kPa (18 psi), with a 0.076 cm air gap width, and the polymerthroughput rate was about 180 g/hr/cm.

[0204] The resulting melt blown polypropylene fabrics were evaluated forantistatic performance, oil repellency, and water repellency using TestMethods III, V, and VI. The results are shown in Tables 9 and 10. TABLE9 Static Charge Dissipation, Oil Repellency, and Water Repellency ofEscorene ™ PP3505 Polypropylene Nonwovens Charge (Kvolts) Static Decay(sec) Repellent Antistat Repellency 10% 25% 50% 10% 25% 50% Ex. No. (Wt%) (Wt %) O W RH RH RH RH RH RH C6 None None 0 2 4.3 5+ 5+ 60+ 60 60 1.71.7 >10 >10 5 5 >10 >10 C7 FR-1 1% None 1 8 WNC WNC WNC WNC WNC WNC C8FR-2 1% None 0 7 NR NR NR NR NR NR C9 FR-3 1.25% None 0 7 NR NR −.5 NRNR >10 C10 FR-4 1% None 1 7 NR NR −.75 NR NR >10

[0205] The results in Table 9 show that polypropylene nonwoven alonelacked oil and water repellency and antistatic properties, and that theaddition of fluorochemical repellents significantly increasedrepellency, particularly the water repellency of polypropylene, but madeno contribution to improvement of antistatic properties. TABLE 10 StaticCharge Dissipation, Oil Repellency, and Water Repellency of Escorene ™PP3505 Polypropylene Nonwovens Repel- Repel- Charge (Kvolts) StaticDecay (sec) Ex. lent Antistat lency 10% 25% 50% 10% 25% 50% No. (Wt %)(Wt %) O W RH RH RH RH RH RH C12 None Antistat 22 0 2 5+ 3.4 5+ 0.860.14 0.03 (1%) 10 FR-1 Antistat 22 2 9 5 5 5 0.6 0.3 0.03 (1%) (1%) 11FR-2 Antistat 22 1 7 5 5 4 0.7 0.3 0.05 (1%) (1%) 12 FR-4 Antistat 22 15 5 5 4 1.3 1.1 0.4 (1%) (1%) C13 None Antistat 16 0 2 5+ 5+ 5+ 0.140.19 0.63 (1%) 13 FR-1 Antistat 16 1.5 9 5 5 5 0.5 0.2 0.2 (1%) (1%) 14FR-3 Antistat 16 1 7 4 4.7 4.5 0.1 0.09 0.1 (1.25%) (1%) 15 FR-4Antistat 16 0 5 4 4.5 4.7 0.6 0.2 2.8 (1%) (1%) C14 None Antistat 16 0 2NR 5 5 NR >10 0.95 (0.5%) 16 FR-1 Antistat 16 1 7 5 5 5 0.5 0.2 0.2 (1%)(0.5%) C15 None Antistat 17 0.5 2 5 5 5 0.90 0.02 0.02 (1%) 17 FR-1Antistat 17 1 8 4.2 4.6 5 8.8 7.3 1.4 (1%) (1%) C16 None Antistat 18 0 25 5 5 4.17 0.09 0.03 (1%) 18 FR-1 Antistat 18 2 9 5 5 5 0.2 0.1 0.04(1%) (1%) C17 None Antistat 19 0 2 NR NR 5 NR NR >10 (1%) 19 FR-1Antistat 19 2 9 5 5 5 0.3 0.1 0.2 (1%) (1%)

[0206] The results in Table 10 together with those in Table 9 show thatthe presence of a combination of a fluorochemical repellent and anoctyldimethyl-2-hydroxyethylammonium anti stat produced excellentantistatic properties with repellency essentially the same as whenrepellent was used alone, and, in some cases, improved the antistaticproperties compared with those found when the antistat was used alone.

Examples 20-26 and Comparative Examples C18-C23

[0207] Antistats 1-4, 20, and 21 alone and in combination with 1 or 1.25weight % Fluorochemical Repellent FR-1 or FR-3 were incorporated intopolypropylene melt blown fibers and processed into nonwoven fabricsessentially as in Examples 10-19 and Comparative Examples C12-C17. Theresulting melt blown polypropylene fabrics were evaluated for antistaticperformance, oil repellency, and water repellency using Test MethodsIII, V, and VI. The results are shown in Table 11. TABLE 11 StaticCharge Dissipation, Oil Repellency, and Water Repellency of Escorene ™PP3505 Polypropylene Nonwovens Repel- Repel- Charge (Kvolts) StaticDecay (sec) Ex. lent Antistat lency 10% 25% 50% 10% 25% 50% No. (wt %)(wt %) O W RH RH RH RH RH RH C18 None Antistat 20 0 2 NR 5+ 5+NR >60 >60 (1%) 20 FR-1 (1%) Antistat 20 1 8 5+ 5+ 5+ 0.01 0.03 0.9 (1%)21 FR-3 Antistat 20 1 8 NR 5+ 4.4 NR 0.02 0.06 (1.25%) (1%) C19 NoneAntistat 21 0 2 NR 4.8 5+ NR 56 >60 (1%) 22 FR-1 (1%) Antistat 21 1.5 9NR 5+ 5+ NR >60 0.9 (1%) C20 None Antistat 1 0 2 5 5 5 0.03 0.03 0.02(1%) 23 FR-1 (1%) Antistat 1 1 9 NR 2.5 2.5 NR >10 0.01 (1%) C21 NoneAntistat 2 0 2 NR NR 5 NR NR >10 (1%) 24 FR-1 (1%) Antistat 2 2 9 NR NR−1.5 NR NR >10 (1%) C22 None Antistat 3 0 2 NR NR 5 NR NR >10 (1%) 25FR-1 (1%) Antistat 3 2 9 NR 0.7 1.5 NR >10 0.01 (1%) C23 None Antistat 40 2 NR 3.7 3.6 NR 60 60 (1%) 26 FR-1 (1%) Antistat 4 1 8 NR 4 4.2 NR 2.811 (1%)

[0208] The results in Table 11 together with those in Table 9 show thatthe combination of fluorochemical repellent and an alkyl ammonium antistat provided essentially the same or better repellency compared withthe repellency obtained when the repellent was used alone. Furthermore,the combination of fluorochemical repellent and antistat often providedsignificantly improved antistatic properties.

Examples 27-34 and Comparative Examples C24-C28

[0209] Antistats 5-9 alone and in combination with 1 or 1.25 weight %Fluorochemical Repellent FR-1 or FR-3 were incorporated intopolypropylene melt blown fibers and processed into nonwoven fabricsessentially as in Examples 10-19 and Comparative Examples C12-C17. Theresulting melt blown polypropylene fabrics were evaluated for antistaticperformance, oil repellency, and water repellency using Test MethodsIII, V, and VI. The results are shown in Table 12. TABLE 12 StaticCharge Dissipation, Oil Repellency, and Water Repellency of Escorene ™PP3505 Polypropylene Nonwovens Repel- Repel- Charge (Kvolts) Decay Rate(sec) Ex. lent Antistat lency 10% 25% 50% 10% 25% 50% No. (wt %) (wt %)O W RH RH RH RH RH RH C24 None Antistat 5 (1%) 0 2 4.8 4.7 5+ 34 8.9 4527 FR-1 Antistat 5 (1%) 1 6 5+ 5+ 5+ 1.3 0.7 1.1 (1%) 28 FR-3 Antistat 5(1%) 0.5 6 5+ 5+ 5+ 0.4 1.3 0.6 (1.25%) C25 None Antistat 6 (1%) 0 2 NR5+ 5+ NR 56 1.01 29 FR-1 Antistat 6 (1%) 1 7 NR 2.7 4.7 NR 5 21 (1%) 30FR-3 Antistat 6 (1%) 1 6 NR 1.3 4.2 NR 0.01 33 (1.25%) C26 None Antistat7 (1%) 0 2 NR 3.6 5+ NR >60 3.98 31 FR-1 Antistat 7 (1%) 1 7 NR 4.3 5+NR >60 9.9 (1%) 32 FR-3 Antistat 7 (1%) 1 6 NR 4.2 5+ NR 36 9.9 (1.25%)C27 None Antistat 8 (1%) 0 2 NR 5+ 4.3 NR 49 0.06 33 FR-1 Antistat 8(1%) 1.5 9 NR 5+ 5+ NR >60 1.5 (1%) C28 None Antistat 9 (1%) 0 2 NR 5+5+ NR >60 0.46 34 FR-1 Antistat 9 (1%) 2 10 NR 5+ 5+ NR >60 0.5 (1%)

[0210] The results in Table 12 together with those in Table 9 show thatthe combination of fluorochemical repellent and alkyl pyridiniumantistat provided essentially the same or better repellency comparedwith the repellency found when the repellent was used alone.Furthermore, the combination of repellent and antistatic compoundprovided significantly improved antistatic properties in some instances.

Examples 35-38 and Comparative Examples C29-C32

[0211] Antistats 10-14 alone and in combination with 1 weight %Fluorochemical Repellent FR-1 were incorporated into polypropylene meltblown fibers and processed into nonwoven fabrics essentially as inExamples 10-19 and Comparative Examples C12-C17. The resulting meltblown polypropylene fabrics were evaluated for antistatic performance,oil repellency, and water repellency using Test Methods III, V, and VI.The results are shown in Table 13. TABLE 13 Static Charge Dissipation,Oil Repellency, and Water Repellency of Escorene ™ PP3505 PolypropyleneNonwovens Repel- Repel- Charge (Kvolts) Decay Rate (sec) Ex. lentAntistat lency 10% 25% 50% 10% 25% 50% No. (wt %) (wt %) O W RH RH RH RHRH RH C29 None Antistat 10 0 2 4.1 3.9 3.4 60+ 0.01 53 (1%) 35 FR-1Antistat 10 2 8 4.7 5 5+ 0.01 0.02 0.03 (1%) (1%) C30 None Antistat 11 02 5+ 5+ 5+ 0.02 20 0.03 (1%) 36 FR-1 Antistat 11 1.5 8 5+ 5+ 5+ 0.7 0.040.03 (1%) (1%) C31 None Antistat 13 0 2 4.5 4.9 4.2 >60 >60 >60 (1%) 37FR-1 Antistat 13 1 8 4.5 5+ 5+ 0.10 0.02 0.10 (1%) (1%) C32 NoneAntistat 14 0 2 NR 3.8 4.4 NR >60 >60 (1%) 38 FR-1 Antistat 14 1 8 4 3.73.6 1.8 0.02 0.01 (1%) (1%)

[0212] The results in Table 13 together with those in Table 9 show thatthe combination of repellent and imidazolium antistat providedessentially the same or better repellency compared with the repellencyfound when the repellent was used alone. Furthermore, the combination ofrepellent and antistat provided significantly improved antistaticproperties.

Example 39 and Comparative Example C33

[0213] Antistat 24 alone and in combination with 1 weight %Fluorochemical Repellent FR-1 was incorporated into polypropylene meltblown fibers and processed into nonwoven fabrics essentially as inExamples 10-19 and Comparative Examples C12-C17. The resulting meltblown polypropylene fabrics were evaluated for antistatic performance,oil repellency, and water repellency using Test Methods III, V, and VI.The results are shown in Table 14. TABLE 14 Static Charge Dissipation,Oil Repellency, and Water Repellency of Escorene ™ PP3505 PolypropyleneNonwovens Charge (Kvolts) Decay Rate (sec) Repellent Antistat Repellency10% 25% 50% 10% 25% 50% Ex. No. (wt %) (wt %) O W RH RH RH RH RH RH C33None Antistat 24 0 2 NR 5+ 5+ NR 25 12 (1%) 39 FR-1 Antistat 24 3 9 54.9 4.3 0.5 0.4 0.6 (1%) (1%)

[0214] The results in Table 14 together with those in Table 9 show thatthe combination of repellent and phosphonium antistat providedessentially the same or better repellency compared with the repellencyfound when the repellent was used alone. Furthermore, the combination ofrepellent and antistat provided significantly improved antistaticproperties.

Example 40 and Comparative Example C34

[0215] Lithium perfluorobutanesulfonate alone and in combination with 1weight % Fluorochemical Repellent FR-1 was incorporated intopolypropylene melt blown fibers and processed into nonwoven fabricsessentially as in Examples 10-19 and Comparative Examples C12-C17. Theresulting melt blown polypropylene fabrics were evaluated for antistaticperformance, oil repellency, and water repellency using Test MethodsIII, V, and VI. The results are shown in Table 15. TABLE 15 StaticCharge Dissipation, Oil Repellency, and Water Repellency of Escorene ™PP3505 Polypropylene Nonwoven Repel- Charge (Kvolts) Decay Rate (sec)Ex. Repellent lency 10% 25% 50% 10% 25% 50% No. (Wt %) Antistat (Wt %) OW RH RH RH RH RH RH C34 None Li+ —OSO₂C₄F₉ 0 2 NR NR 5 NR NR 0 40 FR-1Li+ —OSO₂C₄F₉ 1 6 NR NR 5 NR NR 0.03

[0216] The results in Table 15 together with those in Table 9 show thatthe combination of repellent and lithium perfluorobutanesulfonateantistat provided essentially the same repellency as that found when therepellent was used alone. Furthermore, the combination of repellent andantistat provided essentially the same antistatic properties as thatfound when the antistat was used alone.

Comparative Examples C35-C43

[0217] Aluminum stearate, lithium stearate, and glycerol monostearate incombination with 1 weight % Fluorochemical Repellent FR-1, FR-2, or FR-4was incorporated into polypropylene melt blown fibers and processed intononwoven fabrics essentially as in Examples 10-19 and ComparativeExamples C12-C17. The resulting melt blown polypropylene fabrics wereevaluated for antistatic performance, oil repellency, and waterrepellency using Test Methods III, V, and VI. The results are shown inTable 16. TABLE 16 Static Charge Dissipation, Oil Repellency, and WaterRepellency of Escorene ™ PP3505 Polypropylene Nonwoven Repel- Charge(Kvolts) Decay Rate (sec) Ex. Repellent lency 25% 50% 25% 50% No. (Wt %)Antistat (Wt %) O W RH RH RH RH C35 FR-1 (1%) AlOCO(CH₂)₁₆CH₃ 0 9 NR −1NR >10 (1%) C36 FR-1 (1%) LiOCO(CH₂)₁₆CH₃ 1 9 NR 2.4 NR >10 (1%) C37FR-1 (1%) HOCH2CH(OH)CH2O— 1 9 1.2 0.9 0 >10 CO(CH₂)₁₆CH₃ (1%) C38 FR-2(1%) AlOCO(CH₂)₁₆CH₃ 2 8 NR 2 NR >10 (1%) C39 FR-2 (1%) LiOCO(CH₂)₁₆CH₃1 8 NR −0.5 NR >10 (1%) C40 FR-2 (1%) HOCH2CH(OH)CH2O— 0 5 NR 2 NR >10CO(CH₂)₁₆CH₃ (1%) C41 FR-4 (1%) AlOCO(CH₂)₁₆CH₃ 1 9 NR 0.5 NR >10 (1%)C42 FR-4 (1%) LiOCO(CH₂)₁₆CH₃ 2 6 NR −0.9 NR >10 (1%) C43 FR-4 (1%)HOCH2CH(OH)CH2O— 2 8 NR 2.2 NR >10 CO(CH₂)₁₆CH₃ (1%)

[0218] The results in Table 16 show that neither the nonionic antistaticcompounds nor the ionic antistatic compounds (that lack an anion forwhich the conjugate acid is a strong acid) provided antistaticproperties in combination with fluorochemical repellents.

Example 41 and Comparative Examples C44-C46

[0219] Antistat 16, C₈H₁₇N⁺(CH₃)₂C₂H₄OH ⁻N(SO₂CF₃)₂ (2 weight %) andFluorochemical Repellent FR-1 (2 weight %) were incorporated intoMORTHANE™ PS440-200 urethane melt blown fibers, which were made andprocessed into a nonwoven fabric essentially as described in Examples10-19, except that the extrusion temperature was 230° C. Forcomparisons, MORTHANE™ PS440-200 urethane melt blown fibers withoutantistat or repellent, with Antistat 16 (2 weight %) alone, and withFluorochemical Repellent FR-1 (2 weight %) alone were made and processedinto nonwoven fabrics essentially as described in Comparative ExamplesC7-C 17. The resulting fabrics were tested for antistatic performance,oil repellency, and water repellency, using Test Methods III, V, and VI.The results are shown in Table 17. TABLE 17 Static Charge Dissipation,Oil Repellency, and Water Repellency of Melt Blown MORTHANE ™ PS440-200Urethane Nonwoven Fabrics Repel- Charge (Kvolts) Decay Rate (sec) Ex.Repellent lency 10% 25% 50% 10% 25% 50% No. (Wt %) Antistat (Wt %) O WRH RH RH RH RH RH C44 None None 0 2 NR 5 5 NR >60 >60 C45 None Antistat16 (2%) 0 2 5 5 5 0.09 0.08 0.08 C46 FR-1 (2%) None 6 4 5 5 5 4.20 3.342.4 41 FR-1 (2%) Antistat 16 (2%) 6 7 5 5 5 0.08 0.06 0.07

[0220] The results in Table 17 show that the combination offluorochemical repellent and ionic antistat provided both very goodrepellency and good antistatic properties in polyurethane nonwovenfabric.

Example 42 and Comparative Example C47-49

[0221] Antistat 16 (1 weight %) and Fluorochemical Repellent FR-1 (1weight %) were incorporated into ASPUN™ 6806 poly(ethylene/octene) meltblown fibers, which were made and processed into a nonwoven fabricessentially as described in Examples 10-19, except that the extrusiontemperature was 240° C. For comparisons, ASPUN™ 6806 melt blown fiberswithout any antistat or repellent, with Antistat 16 (1 weight %) alone,and with Fluorochemical Repellent FR-1 (1 weight %) alone were made andprocessed into nonwoven fabrics essentially as described in ComparativeExamples C7-C17. The resulting fabrics were tested for antistaticperformance, oil repellency, and water repellency, using Test MethodsIII, V, and VI. The results are shown in Table 18. TABLE 18 StaticCharge Dissipation, Oil Repellency, and Water Repellency of Melt BlownASPUN ™ 6806 Poly(ethylene/octene) Nonwoven Fabrics Repel- Charge(Kvolts) Decay Rate (sec) Ex. Repellent lency 10% 25% 50% 10% 25% 50%No. (Wt %) Antistat (Wt %) O W RH RH RH RH RH RH C47 None None 0 2 NR NR3 NR NR >60 C48 None Antistat 16 (1%) 0 2 5 5 5 0.07 0.08 0.07 C49 FR-1(1%) None 3 9 NR 1.7 3 NR 0.00 7.68 42 FR-1 (1%) Antistat 16 (1%) 6 7 55 5 0.02 0.01 0.01

[0222] The results in Table 18 show that the combination offluorochemical repellent and ionic antistat provided both very goodrepellency and excellent antistatic properties in poly(ethylene/octene)nonwoven fabric.

Examples 43-45 and Comparative Example 50

[0223] Polypropylene films containing tetrabutylphosphoniumperfluorobutanesulfonate (Antistat 24) and Fluorochemical RepellentFR-1, FR-3, or FR-4 were prepared and evaluated for repellency andantistatic performance. For comparison, a polypropylene film withoutantistat or repellent was essentially identically prepared andevaluated. The melt-blown nonwoven fabrics of Example 39, andComparative Example 7, as well as nonwoven fabrics made essentiallyidentically to Example 39 but with FR-3 and FR-4 substituted for FR-1were pressed into films as follows: About 3.4 g of the folded melt-blownfabric was placed on a steel plate within the perimeter of an 11.2 cm by17.1 cm by 0.177 mm thick shim and covered with another steel plate.This assembly was then placed on a platen press heated to 200° C., withthe platens nearly touching, for about 30 seconds to pre-melt the fabricand allow for escape of air before pressing. Next, the construction wasplaced under 0.91 metric ton of pressure for about one minute. Theassembly was removed from the press and allowed to cool for about 30seconds between two unheated platens. The formed film was then removedfrom the shim and steel plates.

[0224] The resulting films were evaluated for antistatic performance,oil repellency, and water repellency using Test Methods III, V, and VI.The results are shown in Table 19. TABLE 19 Static Charge Dissipation,Oil Repellency, and Water Repellency of Escorene ™ PP3505 PolypropyleneFilms Repel- Charge (Kvolts) Decay Rate (sec) Ex. Repellent lency 10%25% 50% 10% 25% 50% No. (Wt %) Antistat (Wt %) O W RH RH RH RH RH RH C50None None 0 4 NR NR 1.5 NR NR >10 43 FR-1 (1%) Antistat 24 (1%) 2 10 NR5 5 NR >10 1.3 44 FR-3 (1%) Antistat 24 (1%) 1 8 5 5 4.3 >10 2.1 0.7 45FR-4 (1%) Antistat 24 (1%) 1 4 5 5 4.2 4.4 1.6 0.02

[0225] The results in Table 19 show that the combination offluorochemical repellent and phosphonium antistat provided both goodrepellency and good antistatic properties in polypropylene films.

Examples 46-49 and Comparative Examples C51-56

[0226] A polypropylene nonwoven fabric, having a basis weight of 220grams/m², was made essentially as Comparative Example 7, but usingMontell™ H442PP (polypropylene) with the collector speed adjusted forthis basis weight. The resulting fabric was tested for oil repellency,water repellency, and antistatic performance (Test Methods V, VI, andIII) before and after topical treatment with a repellent, various ionicantistats, and combinations of the repellent and antistats. Pad bathsolutions (500 grams) made up of 80 weight % water and 20 weight %isopropanol (IPA) without and with 0.366 weight % repellent (9.15 gramsof 20 weight % solids FC-808 diluted to 500 grams with the 80/20 waterIPA), with 0.366 weight % antistat, and with combinations of 0.366weight % repellent and 0.366 weight % antistat were prepared. A weighed(4-6 grams) piece of nonwoven fabric was dipped in each pad bath andpassed between two 12.7 cm rubber rolls at a pressure of 0.41 MPa and aspeed of 7.6 m/min. The wet fabric was weighed and then dried in aforced air oven at 149° C. for five minutes. The target amount ofrepellent and antistat applied to the fabric was 0.55 weight %. Theactual amount ranged from 0.51 to 0.64%. Repellency and antistaticproperties of the topically treated nonwoven fabric are shown in Table20. TABLE 20 Static Charge Dissipation, Oil Repellency, and WaterRepellency of Topically Treated Polypropylene Nonwovens Repel- Charge(Kvolts) Decay Rate (sec) Ex. Repellent lency 10% 25% 50% 10% 25% 50%No. (Wt %) Antistat (Wt %) O W RH RH RH RH RH RH C51 None None 0 2 5 4.32.2 >10 >10 >10 C52 FC-808 (0.54%) None 6 10 5 NR 5 >10 NR 2.1 C53 NoneAntistat 22 (0.56%) 0 1 5 5 5 1.1 1.3 0.15 46 FC-808 (0.51%) Antistat 22(0.51%) 7 10 5 5 5 .02 .03 .01 C54 None Antistat 23 (0.55%) 0 0 5 5 50.01 0.04 0.01 47 FC-808 Antistat 23 6 10 5 5 5 0.01 0.07 0.01(0.53-0.64%) (0.53-0.64%) C55 None Sodium p- 0 2 NR NR 3.5 NR NR >10Toluenesulfonate (0.55%) 48 FC-808 (0.51%) Sodium p- 6 10 5 5 5 1.5 2.00.1 Toluenesulfonate (0.51%) C56 None Antistat 16 (0.52%) 0 1 5 5 5 2.12.9 1.4 49 FC-808 Antistat 16 8 10 5 5 5 0.01 0.01 0.01 (0.51-0.53%)(0.51-0.53%)

[0227] The results in Table 20 show that surprising and excellentantistatic and repellency properties were obtained by topically treatinga nonwoven with a composition comprising an antistat and afluorochemical repellent.

Example 50 and Comparative Examples C57-C59

[0228] A thermoset epoxy coating was prepared by mixing 5 grams part A(amine part) and 6 grams part B (epoxy part) of Scotchweld™ 1838-iB/ATranslucent Epoxy Adhesive (available from 3M, St. Paul Minn.). Themixture was poured at the top of a 25.5 cm by 15.5 cm by 0.102 mm thickprimed polyester terephthalate film and then drawn over the film using aNo. 12 wire wound (Meyer) bar. The resulting coating was cured at 65° C.for one hour in a forced air oven. The above procedure was repeatedusing separate 5 gram quantities of part A containing 0.33 gram1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (Antistat10), 0.33 gram Fluorochemical Repellent FR-3, and a combination of 0.33gram 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide and0.33 gram Fluorochemical Repellent FR-3, respectively. The curedcoatings were tested for antistatic performance, oil repellency, andwater repellency using Test Methods III, V, and VI. The results areshown in Table 21. TABLE 21 Static Charge Dissipation, Oil Repellency,and Water Repellency of Thermoset Epoxy Coatings Decay Charge RateRepel- (Kvolts) (sec) Ex. Repellent lency 50% 50% No. (Wt %) Antistat(Wt %) O W RH RH C57 None None 1 6 5 >60 C58 None Antistat 10 (2.9%) 1 35 24 C59 FR-3 (2.9%) None 8 10 5 >60 50 FR-3 (2.9%) Antistat 10 (2.9%) 810 5 9.6

[0229] The results in Table 21 show that high oil and water repellencyand some improvement in antistatic properties were obtained by using acombination of a fluorochemical repellent and an ionic antistat in athermoset epoxy coating.

Example 51 and Comparative Examples C60-C62

[0230] A moisture curable polyurethane resin was prepared by combiningone equivalent of LHT 28 (Union Carbide Corp., Danbury, Conn.), oneequivalent of PPG 3025 (ARCO Chemical Co., Newtown Square, Pa.), and 4equivalents of toluene dissocyanate under a dry nitrogen purge. Themixture was heated with stirring at 80° C. for 4 hours and then cooledto 60° C. A few drops of dibutyltin dilaurate was added to the mixture,and the mixture was allowed to come to room temperature.

[0231] A thermoset polyurethane coating was prepared as follows: Aportion of the resulting moisture curable polyurethane resin (10 grams)was heated to about 100° C. using a heat gun. About 2 ml of the heatedresin was pipetted onto the top of a 25.5 cm by 15.5 cm by 0.102 mmthick primed terephthalate polyester film, and the resin was drawn overthe film using a No. 12 Meyer bar. The resulting coating was cured at65° C. for 12 hours in a forced air oven and then allowed to stand atambient conditions for 10 hours. The above procedure was repeated usingseparate 10 gram quantities of urethane resin containing 0.157 gram1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide (Antistat10), 0.153 gram Fluorochemical Repellent FR-3, and a combination of0.157 gram 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imideand 0.151 gram Fluorochemical Repellent FR-3, respectively. The curedcoatings were tested for antistatic performance, oil repellency, waterrepellency, and surface resistivity using Test Methods III, IV, V, andVI. The results are shown in Tables 22 and 23. TABLE 22 Static ChargeDissipation, Oil Repellency, and Water Repellency of Thermoset UrethaneCoatings. Repel- Charge (Kvolts) Decay Rate (sec) Ex. Repellent lency10% 25% 50% 10% 25% 50% No. (Wt %) Antistat (Wt %) O W RH RH RH RH RH RHC60 None None 1 3 5 5 5 2.4 2.4 2.9 C61 None Antistat 10 (1.5%) 1 3 5 55 0.01 0.01 0.01 C62 FR-3 (1.5%) None 8 10 5 5 5 5.4 4.1 2.0 51 FR-3(1.5%) Antistat 10 (1.5%) 8 10 5 5 5 0.05 0.03 0.02

[0232] The results in Table 22 show that high oil and water repellencyand excellent antistatic properties were obtained when a combination offluorochemical repellent and ionic antistat were used in a thermoseturethane coating. TABLE 23 Surface Resistivity of Thermoset UrethaneCoatings Surface Resistivity at 26% RH and Example Repellent Antistat21.7° C. No. (Wt %) (Wt %) (ohms/square) C60 None None >10E12 C61 NoneAntistat 10 (1.5%) 2.67 × 10E10 C62 FR-3 (1.5%) None >10E12 51 FR-3(1.5%) Antistat 10 (1.5%) 1.75 × 10E10

[0233] The results in Table 23 show that an improvement in antistaticproperties was obtained by using a combination of fluorochemicalrepellent and antistat compound in a thermoset urethane coating.

[0234] Various modifications and alterations of this invention willbecome apparent to those skilled in the art without departing from thescope and spirit of this invention.

What is claimed is:
 1. A process for preparing a water- andoil-repellent, antistatic composition comprising the steps of (a)combining (i) at least one nonpolymeric ionic salt consisting of atleast one cation and at least one anion, said cation being selected fromthe group consisting of monovalent metal cations, divalent metalcations, and organic onium cations, and said anion being a weaklycoordinating anion, the conjugate acid of said anion having an aciditygreater than or equal to that of a hydrocarbon sulfonic acid, and withthe proviso that said anion is organic or fluoroorganic when said cationis a metal, (ii) at least one fluorochemical repellent, and (iii) atleast one thermoplastic polymer; and (b) melt processing the resultingcombination.
 2. The process of claim 1 wherein either said ionic salt orsaid fluorochemical repellent is combined with said thermoplasticpolymer, and the other is topically applied to the surface of theresulting melt-processed combination.
 3. A process for preparing awater- and oil-repellent, antistatic composition comprising the steps of(a) combining (i) at least one nonpolymeric ionic salt consisting of atleast one cation and at least one anion, said cation being selected fromthe group consisting of monovalent metal cations, divalent metalcations, and organic onium cations, and said anion being a weaklycoordinating anion, the conjugate acid of said anion having an aciditygreater than or equal to that of a hydrocarbon sulfonic acid, and withthe proviso that said anion is organic or fluoroorganic when said cationis a metal, (ii) at least one fluorochemical repellent, and (iii) atleast one thermosetting polymer or ceramer or the reactive precursors ofsaid polymer or ceramer; and (b) allowing the resulting combination tocure.
 4. A process for preparing a water- and oil-repellent, antistaticcomposition comprising the step of applying a topical treatmentcomposition to at least a portion of at least one surface of at leastone insulating material, said topical treatment composition comprising(a) at least one nonpolymeric ionic salt consisting of at least onecation and at least one anion, said cation being selected from the groupconsisting of monovalent metal cations, divalent metal cations, andorganic onium cations, and said anion being a weakly coordinating anion,the conjugate acid of said anion having an acidity greater than or equalto that of a hydrocarbon sulfonic acid, and with the proviso that saidanion is organic or fluoroorganic when said cation is a metal; and (b)at least one fluorochemical repellent.
 5. The process of claim 4 whereina first topical treatment composition comprises said ionic salt, asecond topical treatment composition comprises said fluorochemicalrepellent, and said first and second topical treatment compositions aresequentially applied to said portion of said surface.
 6. A process forpreparing a water- and oil-repellent, antistatic composition comprisingthe steps of (a) dissolving (i) at least one nonpolymeric ionic saltconsisting of at least one cation and at least one anion, said cationbeing selected from the group consisting of monovalent metal cations,divalent metal cations, and organic onium cations, and said anion beinga weakly coordinating anion, the conjugate acid of said anion having anacidity greater than or equal to that of a hydrocarbon sulfonic acid,and with the proviso that said anion is organic or fluoroorganic whensaid cation is a metal, (ii) at least one fluorochemical repellent, and(iii) at least one insulating material in at least one solvent; (b)casting or coating the resulting solution on at least one substrate; and(c) allowing evaporation of said solvent.
 7. A process for preparing awater- and oil-repellent, antistatic composition comprising the steps of(a) combining (i) at least one nonpolymeric ionic salt consisting of atleast one cation and at least one anion, said cation being selected fromthe group consisting of monovalent metal cations, divalent metalcations, and organic onium cations, and said anion being a weaklycoordinating anion, the conjugate acid of said anion having an aciditygreater than or equal to that of a hydrocarbon sulfonic acid, and withthe proviso that said anion is organic or fluoroorganic when said cationis a metal, (ii) at least one fluorochemical repellent, and (iii) atleast one monomer; and (b) allowing polymerization of the monomer tooccur.